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Very Important Paper

2,6-Diisopropylphenyl-Substituted Bismuth Compounds:Synthesis, Structure, and ReactivityTobias Dunaj,[a] Kevin Dollberg,[a] Christian Ritter,[a] Fabian Dankert,[a] andCarsten von Hänisch*[a]

The 2,6-diisopropylphenyl (Dipp) substituent is introduced todiaryl bismuth chemistry. Dipp2BiBr (1-Br) was prepared by aGrignard reaction and subsequently used as precursor forsynthesis of the other diaryl halido bismuthanes Dipp2BiX (1-X,X=F, Cl, I) and the corresponding triflate Dipp2BiOTf (1-OTf).Moreover, 1,1,2,2-tetrakis(2,6-diisopropylphenyl)dibismuthane(2) was prepared. All isolated compounds were characterizedvia single crystal X-ray diffraction analysis, NMR spectroscopy, IR

spectroscopy, and elemental analysis. Furthermore, the reac-tivity of a dibismuthane towards elemental sulfur was inves-tigated, and the formed dibismuthanyl tri- and pentasulfide(3a, 3b) were characterized by single crystal X-ray analysis.Functionalization of the diaryl halido bismuthanes with LiPtBu2

or tBu2PTMS (TMS=SiMe3) gives access to the interpnictogencompound Dipp2Bi� PtBu2 (4), which shows a rare example of acovalent Bi� P bond.

Introduction

Diaryl halido bismuthanes can be prepared via saltmetathesis,[1–4] or redistribution reactions of two equivalents ofa triaryl bismuthane and a bismuth trihalides.[1,5–10] Moreover,diaryl bismuth halides of the heavier halogens can be preparedvia halogen exchange reactions with alkaline or earth alkalinemetal halides and diaryl bismuth halides of lighterhalogens.[1,11,12] It is common for bismuth halides to showsecondary bonding interactions between bismuth and halogenatoms of neighboring molecules in the solid state.[8–10,12–14] Thetendency for intermolecular interactions lowers when stericallymore demanding substituents are employed.[2,4] Consequently,steric demand greatly influences the solid state structure ofsubstituted halido bismuthanes. Most dialkyl and diaryl halidobismuthanes with low steric bulk around the bismuth centerform one dimensional polymeric chains with alternatingbismuth and halide atoms.[9,10,12–14] Sterically shielded dialkyl anddiaryl halido bismuthanes form monomers,[2,4] dimers[8] oroligomers.[12] The monomeric, 2,6-dimesitylphenyl (Ter) substi-tuted, chloro bismuthane (Ter2BiCl) and the polymeric, mesityl(Mes) substituted, bromo bismuthane (Mes2BiBr) are shown inFigure 1 as examples.

Through reaction of a diaryl or dialkyl halido bismuthanewith alkali and alkaline earth metals dibismuthanes are

obtained via reductive coupling.[3,15–17] Another reaction path-way towards dibismuthanes is the reaction with hydridesources. Here, a secondary bismuthane is produced in the firstreaction step, decomposing to the corresponding dibismuthaneunder elimination of dihydrogen.[18–22] Such dibismuthanes areknown to react with element-element bonds and have success-fully been used for the activation of chalcogens[16,23–26] and evenwhite phosphorus.[19] It was shown recently, that dibismuthanesare also suitable as catalysts in dehydrocoupling reactions.[22]

Recently, we showed that interpnictogen compounds areuseful as precursors for the preparation of doped semiconduc-tors via MOCVD processes.[27–31] Using aryl substituents atbismuth, could give access to interpnictogen compounds thatprove useful as precursors.

In this report, the 2,6-diisoproylphenyl-substituent (Dipp) isintroduced to diaryl bismuthane chemistry. Diaryl halidobismuthanes of all halides (X=F, Cl, Br, I) and the correspondingtriflate compound (Dipp2BiOTf) were prepared and theirstructures were examined. The 1,1,2,2-tetrakis(2,6-diisopropyl-phenyl)dibismuthane was obtained and its reactivity towardselemental sulfur was investigated. Moreover, an interpnictogencompound with a Bi� P bond was obtained by functionalizationof the diaryl halido bismuthanes with LiPtBu2 or tBu2PTMS(TMS=SiMe3).

[a] T. Dunaj, K. Dollberg, C. Ritter, Dr. F. Dankert, Prof. Dr. C. von HänischFachbereich Chemie and Wissenschaftliches Zentrum für Materialwissen-schaften (WZMW)Philipps-Universität MarburgHans-Meerwein-Straße 4, 35043 Marburg, GermanyE-mail: haenisch@chemie.uni-marburg.deSupporting information for this article is available on the WWW underhttps://doi.org/10.1002/ejic.202001019

© 2021 The Authors. European Journal of Inorganic Chemistry published byWiley-VCH GmbH. This is an open access article under the terms of theCreative Commons Attribution Non-Commercial License, which permits use,distribution and reproduction in any medium, provided the original work isproperly cited and is not used for commercial purposes. Figure 1. (a) Monomeric Ter2BiCl. (b) Polymeric Mes2BiBr.

[4,9]

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Results and Discussion

Synthesis of the diaryl halido bismuthanes Dipp2BiX (X=F, Cl,Br, I) and (Dipp2Bi)2

It is reported in the literature, that chlorobis(2,4,6-triisopropyl-phenyl)bismuthane can be prepared from the correspondingGrignard reagent, 2,4,6-triisopropylphenylmagnesium bromide,and BiCl3.

[1] Applying this synthetic protocol, 2,6-diisopropylphe-nylmagnesium bromide was reacted with BiCl3 in THF. Thereaction did not yield the expected chloro bismuthane asreported for the 2,4,6-triisopropylphenyl substituent. Rather thecorresponding bromo-bis(2,6-diisopropylphenyl)bismuthane (1-Br) was obtained as an orange solid in 54% yield. This isprobably due to halide exchange with MgBrCl, produced duringthe reaction. This reaction can easily be performed in a gramscale. Repeating the reaction on a milligram scale using BiBr3,gives a better yield of 67%. Halide exchange reactions are wellknown in aryl and alkyl bismuth chemistry and often applied toobtain iodo bismuthanes.[1,11,12,21,32] Consequently, the (2,6-diisopropylphenyl)iodobismuthane (1-I) was prepared by thereaction of 1-Br with CaI2 in THF at 20 °C and obtained as deepred crystals from pentane solution in 65% yield. The com-pounds 1-Br and 1-I show thermochromism, becoming paleyellow upon cooling to liquid nitrogen temperatures. Moreover,solutions of 1-Br and 1-I are yellow, opposed to the orange orred bulk material. Obtaining the chloro-(2,6-diisopropylphenyl)bismuthane 1-Cl and fluoro-(2,6-diisopropylphenyl)bismuthane1-F from 1-Br via halide exchange reaction was neither possiblewith the sodium, nor the silver halides. Using 1-I in the reactionwith silver fluoride, 1-F can be obtained as colorless solid in66% yield. The solution to obtain the chloro bismuthane, and1-F in higher yield, was the reaction of 1-Br with silver triflate.The corresponding (2,6-diisopropylphenyl)triflatobismuthane 1-OTf was obtained as a yellow solid in 62% yield. Using 1-OTf asprecursor, reaction with NaF or NaCl respectively, gave accessto 1-F and also 1-Cl. Compound 1-F was obtained in 89% and1-Cl in 45% yield (see Scheme 1 for an overview of the hereinsynthesized bismuthanes).

Upon reaction of the sterically shielded Ter2BiCl with ahydride source, the first stable molecular secondary bismuthane

was isolated by Power et al.[4] For sterically less shielded halidobismuthanes, dibismuthanes are obtained in similarreactions.[18–20] Reaction of 1-Br or 1-OTf with NaBHEt3, at� 50 °C in toluene gives a red solution that turns black uponwarming to room temperature. After work up of the reactionmixture, the 1,1,2,2-tetrakis(2,6-diisopropylphenyl)dibismuthane(2) is obtained as black, light sensitive solid in 94% yield. Thered color at the start of the reaction, might be due tothermochromic behavior or indicate formation of the hydrideDipp2BiH, decomposing to 2 at higher temperature. However,the assumed bismuth hydride intermediate could not beisolated or spectroscopically characterized due to lack ofthermal stability. The same behavior was observed in theliterature for the reaction of Mes2BiCl with LiBH4 or LiAlH4, or thereaction of (C2F5)2BiBr and Bu3SnH.

[21,22] Compound 2 showsintense thermochromism, turning bright pink upon cooling toliquid nitrogen temperatures. Diluted solutions of 2 are yellow,turning black upon concentrating the solution.

Reaction of 2 with sulfur

Aryl substituted dibismuthanes are known to react withelemental sulfur, leading to the insertion of a sulfur atom intothe Bi� Bi bond.[16,24,25] Reaction of 2 with 1/8 S8 in α,α,α-trifluortoluene (TFT) did not lead to complete conversion of thedibismuthane, even after stirring for 12 hours. In the nextexperiment, 2 and 2/8 S8 were stirred for 90 minutes in TFT.Complete consumption of the black compound 2 was indicatedby a color change of the reaction mixture, turning yellow. Afterworkup, cooling of a concentrated solution in pentane gavecrystals of a dibismuthanyl tri- (3a) and a pentasulfide (3b)both of which were suitable for single crystal X-ray diffractionanalysis (see Scheme 2). Due to the stoichiometry in thereaction, 3a and 3b must be side products, assuming completeconsumption of 2. The insertion of Sn-chains (n=1, 3, 5) into aBi� Bi single bond is known in the literature for bis(amidodimethyl)disiloxane substituted dibismuthanens, with nbeing depended on steric bulk of the ligands.[23] For solely arylor alkyl substituted dibismuthanes, only the insertion of one

Scheme 1. Synthesis of 1-F, 1-Cl, 1-Br and 1-OTf.Scheme 2. (a) Synthesis of 3a and 3b via reaction of 2 with elemental sulfur.(b) Synthesis of 4 via salt elimination and via silyl-halide abstraction.

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sulfur atom into the Bi� Bi bond is reported so far.[16,24,25] Thereaction of 2 with sulfur shows, that the insertion of a S3 or S5unit is also possible for solely aryl substituted dibismuthanes.The obtained mixture of compounds was examined via 1H NMRspectroscopy, showing at least two different Dipp substitutedcompounds. Unfortunately, the 1H NMR spectrum of the bulkdoes not give insights, which signal sets corresponds to thefound species. It can also not be excluded, that one speciesmight correspond to a single sulfur “S1“-bridged species. So far,it was not possible to obtain 3a or 3b in analytically pure form.

Functionalization with phosphanes

With the earliest mention of a bismuth phosphide complex in1999, examples for covalent Bi� P bonds are very rare in theliterature.[10,19,33–37] The formation of the Bi� P bond is realized bythe reaction of a halido bismuthane and either a lithiumphosphide or silyl phosphane. Upon reaction of 1-Br withLiPtBu2 in pentane, the phosphabismuthane Dipp2BiPtBu2 (4)was obtained. Reaction of 1-Br with PtBu2TMS (TMS=SiMe3) didnot yield the desired product as no reaction was observed,even after several days. Using 1-F though, reaction withPtBu2TMS proceeds smoothly via formation of Me3SiF and 4(see Scheme 2). Red, light and temperature sensitive, crystals,suitable for single crystal X-ray diffraction, were obtained from apentane solution at � 32 °C. The successful synthesis of 4 showsthat the compounds 1-X are indeed useful starting materials forthe formation of new binary group 15 compounds containingbismuth. For application in MOCVD processes, the metalorganic compounds have to be volatile. This is not the case forcompound 4. Nevertheless, the insights gained by the synthesisof 4 will be of use in the preparation of bismuth containinginterpnictogen compounds bearing smaller substituents. Amore detailed analysis of such binary precursor molecules ofgroup 15 elements will be published soon.

Spectroscopic data analysis

The 1H NMR spectra of all compounds 1-X (X=F, Cl, Br, I, OTf)and 4 show one set of signals corresponding to a Dippsubstituent indicating Cs symmetry for the compounds 1-X and4. From heavier to the lighter halogens, the aromatic signals ofthe Dipp substituent are shifted towards a lower field. Thearomatic protons of 1-OTf show an even stronger low field shift.The chemical shift of the ipso-carbon atom in the 13C NMRspectra of compounds 1-X show the same trend (1-I: δ=174.5;1-Br: δ=181.9; 1-Cl: δ=185.6; 1-F: δ=191.1; 1-OTf: 207.6). Thisstrong deshielding indicates a trend in group electronegativityof the Bi� X fragment, lowest in 1-I and highest in 1-OTf. Thedeshielding effect corresponds well with literature known diarylhalido and triflato bismuthanes.[1,5,38–40] The 19F NMR chemicalshift of 1-F (δ= � 215.5) in C6D6 is considerably high field shiftedcompared to literature known diaryl or dialkyl fluoro bismu-thanes (δ= � 171.9 to � 188.7).[21,41,42] This indicates a strongershielding of the fluorine nucleus compared to literature known

compounds. The bismuth atoms of the R2BiF compoundsdescribed in the literature are either coordinated by an intra-molecular lewis-base or NMR spectra were recorded in donatingsolvents like acetonitrile.[21,41,42] To exclude, that the high fieldshift in the 19F NMR spectrum is attributed to the use of a donorfree deuterated solvent, spectra of 1-F were also measuredusing CD3CN as a solvent. The chemical shift in the 19F NMRspectrum (δ= � 213.1 ppm) is almost identical to that in C6D6,indicating no coordination of CD3CN to the bismuth centre dueto the steric demand of the Dipp substituents. Compound 4shows the expected signals for the Dipp substituents in the 1Hand 13C NMR-spectra. The 31P NMR spectrum shows abroadened signal at 84.3 ppm, matching well to other literatureknown dialkyl phospha bismuthanes.[10,19,36]

In the MS spectra, a signal corresponding to the ionizedmolecular species was observed for 1-Br, 1-I and 1-OTf,although only of low intensity. For 2 and 4 signals correspond-ing to fragments arising from Bi� Bi or Bi� P bond cleavage areobserved. The main signals in all recorded spectra correspondto the fragments Dipp2Bi

+ and DippBi+, showing that cleavageof the Bi� X bond is favored, compared to the Bi� C bond.

The IR spectra of the isolated components show theexpected bands for the Dipp substituent. For 1-OTf additionalbands for SO stretching modes are identified at 1332, 1100 and975 cm� 1. Moreover, bands for the stretching vibrations of theCF3 group are observed at 1190 and 1160 cm� 1. The positions ofthe SO bands fits to a covalently bound triflate anion.[43–47] Thiswas confirmed by single crystal X-ray diffraction.

Single crystal X-ray analysis

Compound 1-F crystalizes in the monoclinic space group P21/cwith Z=4. The intramolecular Bi1-F1 bond length has a value of211.5(3) pm. Moreover, a secondary bonding interactionbetween the fluoride atom and a bismuth atom of aneighboring molecule with a Bi1-F1’ distance of 304.6(3) pm isobserved. This value is clearly smaller than the sum of the vander Waals radii (354 pm).[48,49] This results in one dimensionalpolymer strings of alternating Bi and F atoms along thecrystallographic c-axis (Figure 2) with alternating short and longBi� F distances. There are only few structurally described dialkylor diaryl fluoro bismuthanes in the literature,[21,41,42] with 1-Fbeing the first donor free compound. To the best of ourknowledge, 1-F shows the shortest intramolecular Bi� F bond ofa Bi(III) compound so far. Like 1-F, the compounds(C2F5)2BiF·acetone

[21] and [MeO-(C2H4)-N(CH2C6H4)2]BiF[42] form

polymer chains in the solid state. Due to less steric demand, theintra- and intermolecular Bi� F bond lengths in(C2F5)2BiF·acetone are almost equal in length (222.9(2) and226.2(2) pm).[21] Thus the intramolecular Bi� F bond length in 1-Fis shorter, while the intermolecular bond length is much longer.In [MeO-(C2H4)-N(CH2C6H4)2]BiF, the Bi atom is coordinatedintramolecularly by N and O leading to longer intra- andintermolecular Bi� F bond lengths of 221.3(4) and 358.8(5)pm,[42] compared to 1-F. With an Bi1-F1-Bi1’ angle of 175.8(1)°,the fluorine atoms in 1-F are almost linearly coordinated. The

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F1-Bi1-F1’ angle is 158.3(1)°, which results in a seesawcoordination of the bismuth atom. The F1-Bi1-C1 angle isslightly larger compared to the F1-Bi1-C2 angle (96.4(2)° vs.92.0(2)°). This is most likely a consequence of steric repulsion ofthe isopropyl group of one Dipp substituent and the fluorineatom.

The compounds 1-Cl and 1-Br crystallize isostructural in thetrigonal space group R�3 with Z=18 and do not form one-dimensional strings. Instead, hexamers containing a ring ofalternating Bi and X (X=Cl, Br) atoms are formed (Figure 3). TheBi� Cl bond length of 255.15(9) pm in 1-Cl is longer than in themonomeric (2,6-Mes2H3C6)2BiCl (248.3(3) pm),[4] but smaller than

in polymeric Ph2BiCl (274.6(4) pm).[13] With 387.7(1) pm, theintermolecular Bi� Cl’ distance is far larger than in Ph2BiCl(276.3(3) pm)[13] and even slightly larger than the sum of thevan der Waals radii (382 pm).[48,49] Hence, it is questionable,whether the formation of oligomers in the solid state can betraced to coulomb interactions between molecules or if theyplay no decisive role in structure formation. The intramolecularBi� Br bond length of 270.19(6) pm in 1-Br corresponds well tothe literature known in Mes2BiBr (269.6(2) pm).[9] Contrary, theintermolecular Bi� Br’ distance of 387.71(7) pm is elongatedcompared to Mes2BiBr (379.5(3) pm),[9] but still beneath the sumof van der Waals radii (390 pm).[48,49] As in 1-F, the longintermolecular Bi� X distances are attributed to the stericdemand of the two Dipp substituents around the Bi atom. With131.49(3)° (1-Cl) and 129.35(2)° (1-Br), the Bi� X� Bi’ bond anglesare significantly smaller than in the previously discussed 1-F.Same holds true for the Br� Bi� Br’ angles. With 134.90(3)° (1-Cl)and 134.13(2)° (1-Br), the X� Bi� X’ angle in the seesawcoordinated bismuth atom also becomes smaller, compared to1-F. Similarly to 1-F, the steric demand of the Dipp substituentleads to one large C� Bi� X angle (1-Cl: 108.60(8)° vs. 92.84(8)°;1-Br: 110.21(6)° vs. 92.66(7)°). As expected, this effect becomesmore pronounced for the heavier and larger halides. Theorange 1-Br shows thermochromism, yielding a pale yellowsolid upon cooling to liquid nitrogen temperatures. Investiga-tion via temperature dependent powder X-ray diffraction andcooling to up to � 170 °C did not show phase transitions. TheXRD patterns can be found in the supplementary information.

Compound 1-I crystalizes in the monoclinic space groupP21/n with Z=4. The Bi� I bond length of 289.74(4) pmcorresponds well with other donor free dialkyl and diaryl iodobismuthanes, forming weak intermolecular bonds (278.5–286.9 pm).[10,21,38] In contrast to the other halogen compounds 1-X (X=F, Cl, Br) and many literature-known diaryl or dialkyl iodobismuthanes,[10,12,21] 1-I does not show secondary intermolecularinteractions of bismuth and halogen atoms. Rather, dimers withshort Bi� Bi’ contacts of 396.54(4) pm are formed in the solidstate (see Figure 4). The Bi� Bi’ distance in this dimer isconsiderably shorter than the sum of the van der Waals radii(414 pm).[48] Short intermolecular Bi� Bi’ distances in the solidstate are not unheard of in the literature. Reported dimericcompounds with short Bi� Bi contacts in the crystal structureinclude Me3Bi (389.9(1) pm),[50] (m-(C2H4)C6H5)3Bi (395.94(5)pm)[51] or [Ph-(C2H4)-N(CH2C6H4)2]BiCl (397.39(9) pm).[42] It wasshown via coupled cluster and dispersion corrected DFTmethods, that the secondary bonding interaction in Me3Bi isdispersion-dominated.[50] The weak interaction within dimers ofthe pnictogen trihalides was also subject of a theoretical study.It is reported that binding interactions in these compounds aredispersion dominated, but also show significant ioniccontribution.[52] Consequently, it can be assumed that the Bi� Biinteraction in 1-I is also mostly dispersion dominated. Using theBi� Bi bond length in the dibismuthane 2 for the calculation ofthe ratio between the Bi� Bi distance in 1-I and a Bi� Bi singlebond, a value of 1.31 is obtained. According to Breunig et al.,compounds with short Pn-Pn contacts, where this ratio is lowerthan 1.4, show thermocromism.[52] This also holds true for 1-I,

Figure 2. Molecular structure of 1-F in the solid state. Hydrogen atoms areomitted and Dipp substituents are shown as wire model for clarity. Ellipsoidsare shown at a 50% probability level. Molecules corresponding to atomslabelled with an apostrophe are symmetry generated using x, 1/2� y, 1/2+ zand x, 1/2� y, � 1/2+ z. Selected bond lengths (pm) and angles (deg): Bi1-F1211.5(3); Bi1-F1’ 304.6(3); Bi1-C1 228.6(6); Bi1-C2 229.3(6); C1-Bi1-C2 97.2(2);F1-Bi1-C1 92.0(2); F1-Bi1-C2 96.4(2), Bi1-F1-Bi1’ 175.8(1); F1-Bi1-Bi1’ 158.3(1).

Figure 3. Structure of the hexamer formed by 1-Br in the solid state withview along the crystallographic and b-axis. Hydrogen atoms are omitted andthe Dipp substituents are shown as wire model for clarity. Ellipsoids areshown at a 50% probability level. Molecules not labelled or correspondingto atoms labelled with an apostrophe are symmetry generated using 1/3+x,2/3� x+y, 2/3� z; 1� xvy, 1� x, z; 4/3� x, 2/3� y, 2/3� z; 1� y, x� y, z; 1/3+x� y, � 1/3+x, 2/3� z. Compound 1-Cl crystallizes isostructural. Selectedbond lengths (pm) and angles (deg) for 1-Br: Bi1-Br1 270.19(6); Bi1-Br1’387.71(7); Bi1-C1 229.2(3); Bi1-C2 228.2(3); C1-Bi1-Br1 110.31(7); C2-Bi1-Br192.66(7); C1-Bi1-C2 96.8(1); Bi1-Br1-Bi1’ 129.35(2); Br1-Bi1-Br1’ 134.13(2).Selected bond lengths (pm) and angles (deg) for 1-Cl: Bi1-Cl1 255.15(9); Bi1-Cl1’ 387.7(1); Bi1-C1 228.1(4); Bi1-C2 229.4(3); C1-Bi1-Cl1 92.84(8); C2-Bi1-Cl1108.60(8); C1-Bi1-C2 96.3(1); Bi1-Cl1-Bi1’ 131.49(3); Cl1-Bi1-Bi1’ 134.90(3).

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changing color from deep red at room temperature to paleyellow at liquid nitrogen temperatures.

Compound 1-OTf crystalizes in the monoclinic space groupP21/n with Z=4. The Bi� O bond length of 231.9(1) pm issignificantly shorter than in the corresponding Ph2BiOTf(253.1(6) pm).[39] The literature known Ph2BiOTf forms one

dimensional polymers with multiple inter- and intramolecularshort contacts, explaining the elongation of the Bi� O bond.Contrary, 1-OTf forms dimers via intermolecular secondarybonding interactions of a second oxygen atom of a triflateanion and a neighboring bismuth atom (Figure 5). This bridgingmotif is known for several bismuth compounds with examplesincluding Mes(o-(Me2N(CH2))C6H4)BiOTf or (o-(tBuO)2C6H3)BiOTf2).

[44,54] The intermolecular Bi� O distance of 349.8(2) pm isslightly shorter than the sum of the van der Waals radii(359 pm).[48,49] The formation of a dimeric structure with fewerbut shorter Bi� O contacts is caused by steric shielding of the Biatoms through the bulky Dipp substituents. As in the previouscompounds, the Bi atom is coordinated by four substituents ina seesaw manner with an O1-Bi1-O2’ angle of 150.39(4)°.

Compound 2 crystalizes in the monoclinic space group C2/cwith Z=4 with half a molecule representing the asymmetricunit (Figure 6). With 302.02(2) pm, the Bi� Bi bond length issimilar to related compounds like (Ph2Bi)2 (299.0(2) pm) or(Mes2Bi)2 (308.7(3) pm) described in the literature.[20,55] The Bi� Cdistances and the angles around the bismuth center correspondwell with the previously discussed compounds. Compound 2shows intense thermocromism, turning bright pink whencooled to liquid nitrogen temperatures.

An inseparable mixture of products was obtained byreaction of 2 with sulfur. Two species, the trisulfide and thepentasulfide, were identified via single crystal X-ray analysisafter choosing crystals from the mixture mechanically. Due tosimilar color and habitus, bulk material of 3a and 3b could notbe obtained separately. The trisulfide 3a crystalizes in themonoclinic space group P21/c with Z=4 (Figure 7) and the

Figure 4. Molecular structure of the 1-I dimer in the solid state. Hydrogenatoms are omitted and Dipp substituents are shown as wire model forclarity. Ellipsoids are shown at a 50% probability level. Moleculescorresponding to atoms labelled with an apostrophe are symmetrygenerated using 1� x, 1� y, 1� z. Selected bond lengths (pm) and angles(deg): Bi1-I1 289.74(4); Bi1-C1 229.8(2); Bi1-C2 229.3(3); Bi1-Bi1’ 396.54(4); C1-Bi1-I1 111.67(7); C2-Bi� I1 95.70(6); C1-Bi� C2 96.20(9); I1-Bi1-Bi1’ 85.29(1).

Figure 5. Molecular structure of the 1-OTf dimer in the solid state. Hydrogenatoms are omitted and Dipp substituents are shown as wire model forclarity. Ellipsoids are shown at a 50% probability level. Moleculescorresponding to atoms labelled with an apostrophe are symmetrygenerated using 1� x, 1� y, 1� z. Selected bond lengths (pm) and angles(deg): Bi1-O1 231.9(1); Bi1-C1 226.7(2); Bi1-C2, 226.8(2); Bi1-O2’ 349.8(2); C1-Bi1-O1 99.66(5); C2-Bi� O1 90.49(5); C1-Bi� C2 97.61(6); O1-Bi1-O2’ 150.39(4).

Figure 6. Molecular structure of 2 in the solid state. Hydrogen atoms areomitted and Dipp substituents are shown as wire model for clarity. Ellipsoidsare shown at a 50% probability level. Molecules corresponding to atomslabelled with an apostrophe are symmetry generated using 1� x, y, 3/2� z.Selected bond lengths (pm) and angles (deg): Bi1-Bi1’ 302.02(2); Bi1-C1231.8(2); Bi1-C2 232.2(2); C1-Bi1-Bi1’ 91.14(5); C2-Bi� Bi1’ 111.66(6); C1-Bi� C294.97(8).

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pentasulfide 3b in the orthorhombic space group Pbcn withZ=4 with only half a molecule representing the asymmetricunit (Figure 8). Within the standard deviation, the S� S bondlengths and S� S� S angles in 3a and 3b correspond well withthe average bond lengths and angles in elemental S8.

[56–58] Witha bond length of 258.6(1) pm and 258.8(1) pm, the Bi� S bondlength in 3a fit in with other literature known Bi� S bonds ofcompounds with an (Ar2Bi)2Sn (n=1, 3, 5; (252–260 pm))structure.[20,59] In comparison, the Bi� S bond of 3b (260.1(2) pm)is slightly longer. An example for a longer Bi� S bond than in 3bis described in one compound of the form RBi-(S5)2-BiR (R=o-(CH2NMe2)2C6H3) showing a twelve membered Bi2S10 ring,

stabilized by NCN-type pincer ligands at the bismuth atoms(Bi� S: 275–277 pm). The authors ascribe the elongated bondlength to a polarized Bi� S bond, with the positive charge at thebismuth atoms being stabilized by the pincer ligand.[60] TheC� Bi� S angles around the bismuth atom are similar as in thepreviously discussed Dipp substituted structures (Dipp2BiX,X=Cl, Br) with each Bi atom showing one small (3a: 94.3(1)°,90.7(1)°; 3b: 90.2(2)°) and one larger (3a: 108.2(1)°, 110.2(1)°;3b: 104.5(1)°) angle due to steric repulsion of the polysulfidechain and one Dipp substituent. The Bi� Bi’ distance in 3b is442.40(5) pm, far larger than the sum of the van der Waals radii(414 pm),[49] indicating no interaction between the bismuthatoms.

Compound 4 crystalizes in the triclinic space group P�1 withtwo molecules in the asymmetric unit (Figure 9). The Bi� P bondin 4 (269.80(7) pm and 270.14(7) pm) is slightly elongatedcompared to most literature known neutral phosphabismu-thanes (258.9(2)–269.5(7) pm).[10,19,33–37] The elongation is mostlikely a result of the sterically shielding Dipp substituents. Thesteric demand also reflects in the large C1-Bi1-P1-C3 torsionangles of 106.97 (9) °.

Conclusion

The Dipp substituent is introduced to diaryl bismuth chemistry.The respective diaryl halido bismuthanes 1-X (X=F, Cl, Br, I)were prepared and fully characterized. Their solid statestructures were examined via single crystal X-ray diffraction andit was shown that the solid state structure is strongly depended

Figure 7. Molecular structure of 3a in the solid state. Hydrogen atoms areomitted and Dipp substituents are shown as wire model for clarity. Atomslabelled with an apostrophe are symmetry generated using 1� x, y, 3/2� z.Ellipsoids are shown at a 50% probability level. Selected bond lengths (pm)and angles (deg) for 3a: Bi1-S1 258.6(1); Bi2-S2 258.8(1); Bi1-C1 228.3(3); Bi1-C2 229.6(4); Bi2-C3 228.5(4); Bi2-C4 229.9(4); S1-S3 204.7(2); S2-S3 206.1(2);C1-Bi1-S1 94.3(1); C2-Bi1-S1 108.2(1); C1-Bi1-C2 93.8(1); Bi1-S1-S3 93.9(6); C3-Bi2-S2 90.7(1); C4-Bi2-S2 110.2(1); C3-Bi2-C4 95.3(1); Bi2-S2-S3 97.4(6); S1-S3-S2 106.9(9).

Figure 8. Molecular structure of 3b in the solid state. Hydrogen atoms areomitted and Dipp substituents are shown as wire model for clarity. Atomslabelled with an apostrophe are symmetry generated using 1� x, y, 3/2� z.Ellipsoids are shown at a 50% probability level. Selected bond distances(pm) and angles (deg) for 3b: Bi1-S1 260.1(2); Bi1-C1 228.1(6); Bi1-C2229.5(5); S1-S2 204.3(2); S2-S3 206.3(2); C1-Bi1-S1 90.2(2); C2-Bi1-S1 104.5(1);C1-Bi1-C2 94.6(2); Bi1-S1-S2 101.11(8); S1-S2-S3 107.74(9); S2-S3-S2’105.95(7).

Figure 9. Molecular structure of 4 in the solid. One of two molecules of theasymmetric unit are shown. Hydrogen atoms are omitted and Dipp and tBusubstituents are shown as wire model for clarity. Ellipsoids are shown at a50% probability level. Selected bond lengths (pm) and angles (deg) for 4:Bi1-P1 269.80(7); Bi1A-P1A 270.14(7); Bi1-C1 232.1(2); Bi1A-C1A 233.8(2); Bi1-C2 230.5(2); Bi1A-C2A 231.4(2); P1-C3 192.0(2); P1A-C3A 191.2(2); P1-C4190.6(2); P1A-C3A 190.4(2); C1-Bi1-C2 95.09(7); C1A-Bi1A-C2A 95.91(7); C1-Bi1-P1 108.5(5); C1A-Bi1A-P1A 107.99(5); C2-Bi1-P1 104.01(5); C2A-Bi1A-P1A104.52(5); C3-P1-C4 109.03(9); C3A-P1A-C4A 109.34(9); C3-P1-Bi1 95.69(6);C3A-P1A-Bi1A 95.71(7); C4-P1-Bi1 102.58(6); C4A-P1A-Bi1A 103.55(7).

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on the respective halogen atom attached to the bismuth center.While 1-F forms one dimensional polymers, hexamers areformed in the solid state by 1-Cl and 1-Br. Compound 1-I showsa dimeric structure in the solid state. Surprisingly, no secondaryinteraction between iodine and bismuth was observed. Rathershort intermolecular Bi� Bi contacts are formed. Furthermore,the corresponding triflate compound 1-OTf was prepared, fullycharacterized, and successfully used as a precursor for thesynthesis of 1-F and 1-Cl. Via reaction of 1-Br and sodiumsuperhydride, the dibismuthane 2 was obtained. Its reactivitytowards elemental sulfur was studied, leading to a mixture ofproducts. In contrast to previously reported reactions of purelyaryl- or alkyl- substituted dibismuthanes with sulfur, an Sn-chain(n=3, 5) was inserted into the Bi� Bi bond, rather than a singlesulfur atom.[16,24,25] The dibismuthanyl tri- and pentasulfide (3a,3b), were characterized via single crystal X-ray analysis. Theability of 2 to activate element-element bonds should befurther examined to activate other chalcogens or even P4. Thediaryl halido bismuthanes were further functionalized tocompound 4 under formation of a covalent Bi� P bond. Thereaction proceeds either via salt metathesis or trimethylsilylfluoride abstraction. Compounds similar to 4 bearing abismuth-pnictogen-bond could prove useful as single-source-precursors in MOCVD processes. Even though 4 is not volatileenough to be of use in MOCVD processes, its synthesis givesinsides for the preparation of interpnictogen compoundscontaining bismuth. Systematic investigation of interpnictogencompounds with diaryl and dialkyl bismuth fragments and ahigher vapor pressure as well as their application in MOCVDprocesses will be subject to future research.

Experimental SectionGeneral Procedure. All manipulations were carried out under argonatmosphere and exclusion of light using standard Schlenktechnique. All solvents used in the reactions and for crystallizationswere dried via standard techniques, distilled, and stored underargon.[61] Solvents were never stored longer than three weeksbefore use. DippBr, used for the preparation of DippMgBr·THF,tBu2PLi and tBu2PTMS were prepared according to literature knownprocedures.[62–64] The 2,6-Diisopropylaniline (TCI), tBu2PH (Aldrich), n-BuLi in hexane (Aldrich), Me3SiCl (Aldrich), Mg (ITW), CaI2 (Aldrich),AgOTf (Aldrich), NaF (Aldrich), NaCl (ITW), NaBHEt3 in toluene (AlfaAesar) and sulfur (Strem) were used as received. BiCl3 (Strem) wasfreshly sublimed under reduced pressure before use in synthesis.NMR spectra were recorded using a Bruker Avance II 300 MHz and aBruker Avance III 500 MHz spectrometer. The IR-spectra wererecorded on a Bruker FT-IR spectrometer using the attenuated totalreflectance (ATR) mode. For mass spectrometry (CI), a Jeol AccuTOFGCv was used. Elemental analysis was performed on a VarioMicroCube.

Synthesis of Dipp2BiBr (1-Br). BiCl3 (6.00 g, 19.02 mmol) aredissolved in 50 ml THF and added dropwise to a solution ofDippMgBr·THF (15.0 g, 44.43 mmol) in 50 ml THF at 0 °C. Thereaction mixture is allowed to warm to room temperature andstirred overnight. After removal of volatile components underreduced pressure, the solid residue is suspended in pentane andfiltered. Through concentration of the solution and cooling to� 32 °C, 1-Br is obtained as crystalline orange solid. Yield 54%.Elemental analysis for C24H34BiBr calcd: C, 47.15; H, 5.61; found: C,

47.38; H, 5.61; 1H NMR (500 MHz, C6D6) δ: 7.41 (d, 3JH-H=7.6 Hz, 4H,m-CH), 7.24 (t, 3JH-H=7.6 Hz, 2H, p-CH), 3.31 (sept, 3JH-H=6.6 Hz, 4H,CH(CH3)2), 1.11 (d, 3JH-H=6.6 Hz, 12H, CH(CH3)2), 1.06 (d, 3JH-H=

6.6 Hz, 12H, CH (CH3)2);13C{1H} NMR (125 MHz, C6D6) δ: 181.9 (s,

Bi� C), 156.5 (s, m-C), 129.5 (s, p-C), 127.9 (s, o-C), 38.9 (s, CH(CH3)2),25.1 (s, CH(CH3)2), 24.4 (s, CH(CH3)2); IR (cm� 1): 3045 (w), 2958 (m)2923 (w) 2861 (w), 1568 (w), 1458 (w), 1446 (w), 1413 (w), 1382 (w),1363 (w), 1344 (w), 1259 (w), 1234 (w), 1176 (w), 1098 (w), 1043 (w),1001 (w), 928 (w), 796 (s), 728 (m); HR-MS: CI(+) m/z 611.1515 [M+

H]+; calcd 611.1726

Synthesis of Dipp2BiI (1-I). Compound 1-Br (200 mg, 0.32 mmol)and CaI2 (566 mg, 1.93 mmol) were suspended in 20 ml THF andstirred over 12 h at room temperature. After removal of volatilesunder reduced pressure and 40 ml of pentane were added to theremaining solid. The solution was filtered and the filtrate wasconcentrated. By cooling to � 32 °C, red crystals of 1-I wereobtained. Yield 62%. Elemental analysis for C24H34BiI calcd: C, 43.78;H, 5.21; found: C, 43.78; H, 5.22; 1H NMR (300 MHz, C6D6) δ: 7.36 (d,3JH-H=7.6 Hz, 4H, m-CH), 7.21 (t, 3JH-H=7.6 Hz, 2H, p-CH), 3.32 (sept,3JH-H 7 Hz, 4H, CH(CH3)2), 1.11 (d, 3JH-H=6.6 Hz, 12H, CH(CH3)2), 1.06(d, 3JH-H=6.7 Hz, 12H, CH(CH3)2);

13C{1H} NMR (75 MHz, C6D6) δ: 174.5(s, Bi� C), 156.7 (s, m-C), 130.1 (s, p-C), 127.8 (s, o-C), 41.0 (s,CH(CH3)2), 25.6 (s, CH(CH3)2), 24.9 (s, CH(CH3)2); IR (cm� 1): 3040 (w),2958 (m), 2924 (w), 2863 (w), 1569 (w), 1457 (m), 1444 (m), 1411(w), 1382 (w), 1360 (w), 1260 (m), 1233 (w), 1097 (m), 1045 (m),1019 (m), 998 (m), 798 (s), 728 (m); HR-MS: CI(+) m/z 657.1437[M� H]+; calcd 657.1431

Synthesis of Dipp2BiOTf (1-OTf). Compound 1-Br (2.2 g,3.53 mmol) and AgOTf (1.00 g, 3.89 mmol) are suspended in 150 mlpentane and stirred over 72 h at room temperature. After removalof the solvent under reduced pressure, the remaining solid issuspended with 150 ml of toluene and filtered. Volatiles areremoved under reduced pressure and the remaining yellow solid iswashed two times with 20 ml pentane. Crystals suitable for X-raydiffraction were grown from a pentane/toluene mixture at 5 °C.Yield 62%. Elemental analysis for C25H34BiF3O3S calcd: C, 44.12; H,5.04; found: C, 44.02; H, 4.94; 1H NMR (500 MHz, C6D6) δ: 7.62(d, 3JH-H=7.6 Hz, 4H, m-CH), 7.31 (t, 3JH-H=6.6 Hz, 2H, p-CH), 2.76(sept, 3JH-H=6.6 Hz, 4H, CH(CH3)2), 1.06 (d, 3JH-H=6.6 Hz, 24H,CH(CH3)2);

13C{1H} NMR (125 MHz, C6D6) δ: 207.6 (s, Bi� C), 156.5 (s,m-C), 130.3 (s, p-C), 129.7 (s, o-C), 37.2 (s, CH(CH3)2), 23.9 (s,CH(CH3)2); IR (cm� 1): 3046 (w), 2996 (w) 2927 (w) 2868 (w), 1569 (w),1462 (w), 1441 (w), 1388 (w), 1332 (m), 1190 (s), 1160 (m), 1100 (m),1028 (w), 975 (s), 931 (w), 802 (w), 756 (w), 720 (w), 628 (s), 584 (w),529 (w), 512 (w); HR-MS: CI(+) m/z 531.2472 [M� OTf]+; calcd531.2464

Synthesis of Dipp2BiF (1-F). Compound 1-OTf (400 mg, 0.59 mmol)and NaF (172 mg, 2.94 mmol) are suspended in 20 ml THF andstirred 12 h at room temperature. After removal of volatiles underreduced pressure, the remaining solid is taken up in 40 ml oftoluene. The solution is filtered and all volatiles of the filtrate areremoved under reduced pressure. The remaining residue is washedwith cold pentane to obtain 1-F as colorless solid. Crystals suitablefor single crystal X-ray diffraction analysis are obtained from asolution of 1-F in a pentane/ethanol mixture and cooling to � 32 °C.Yield 89%. Elemental analysis for C24H34BiF calcd: C, 52.36; H, 6.23;found: C, 51.96; H, 6.30; 1H NMR (300 MHz, C6D6) δ: 7.45 (d, 3JH-H=

7.6 Hz, 4H, m-CH), 7.30 (t, 3JH-H=7.6 Hz, 2H, p-CH), 3.24 (sept, 3JH-H=

6.7 Hz, 4H, CH(CH3)2), 1.12 (br s, 24H, CH(CH3)2);13C{1H} NMR

(125 MHz, C6D6) δ: 191.1 (d, 2JC-F=15.3 Hz, (s, Bi� C)), 156.4 (s, m-C),129.5 (s, p-C), 128.2 (s, o-C), 35.9 (s, CH(CH3)2), 25.0 (s, CH(CH3)2), 24.4(s, CH(CH3)2);

19F NMR (280 MHz, C6D6) δ: � 215.5 (s, Bi� F); 1H NMR(250 MHz, CD3CN) δ: 7.56 (d, 3JH-H=7.6 Hz, 4H, m-CH), 7.41 (t, 3JH-H=

7.6 Hz, 2H, p-CH), 3.13 (sept, 3JH-H=6.6 Hz, 4H, CH(CH3)2), 1.07(d, 3JH-H=6.6 Hz, 24H, CH(CH3)2);

19F NMR (235 MHz, CD3CN) δ:

Full Papersdoi.org/10.1002/ejic.202001019

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� 213.1 (s, Bi� F); IR (cm� 1): 3047 (w), 2962 (m), 2923 (m), 2865 (w),1569 (w), 1460 (m), 1447 (m), 1417 (w), 1381 (m), 1357 (w), 1261(w), 1236 (m), 1194 (w), 1177 (w), 1160 (w), 1146(w), 1098 (w), 1046(m), 1013 (m), 1006 (w), 929 (w), 797 (s), 729 (s), 633 (m), 495 (w),446 (m), 412 (m); HR-MS: CI(+) m/z 531.2457 [M� F]+; calcd531.2464

Synthesis of Dipp2BiCl (1-Cl). Compound 1-OTf (90 mg, 0.13 mmol)and NaCl (77 mg, 1.32 mmol) is suspended in 10 ml THF and stirredover 12 h at room temperature. After removal of volatiles underreduced pressure, the remaining solid is taken up in 20 ml pentane.The solution is filtered and all volatiles are removed under reducedpressure. The remaining residue is washed with cold pentane toobtain 1-Cl as a yellow solid. Crystals suitable for single crystal X-raydiffraction analysis are obtained from an oversaturated solution of1-Cl in pentane at room temperature. Yield 45%. Elemental analysisfor C24H34BiCl calcd: C, 50.84; H, 6.04; found: C, 50.60; H, 6.04;

1HNMR (500 MHz, C6D6) δ: 7.43 (d, 3JH-H=7.6 Hz, 4H, m-CH), 7.26(t, 3JH-H=7.6 Hz, 2H, p-CH), 3.29 (sept, 3JH-H=6.7 Hz, 4H, CH(CH3)2),1.12 (d, 3JH-H=6.6 Hz, 12H, CH(CH3)2), 1.07 (d, 3JH-H=6.7 Hz, 12H,CH(CH3)2);

13C{1H} NMR (125 MHz, C6D6) δ: 185.6 (s, Bi� C), 156.6 (s,m-C), 129.5 (s, p-C), 128.3 (s, o-C), 38.0 (s, CH(CH3)2), 25.2 (s,CH(CH3)2), 24.4 (s, CH(CH3)2); IR (cm� 1): 3046 (w), 2961 (m), 2923 (w),2862 (w), 1569 (w), 1458 (w), 1446 (w), 1413 (w), 1382 (w), 1363 (w),1259 (s), 1084 (s), 1013 (s), 928 (w), 865 (w), 793 (s), 728 (m), 701(m), 661 (w), 495 (w)

Synthesis of (Dipp2Bi)2 (2). A 1 M solution of NaBHEt3 (0.64 ml,0.64 mmol) in toluene is added to a solution of 1-Br (400 mg,0.64 mmol) in 50 ml toluene cooled to � 78 °C. The reaction mixtureis allowed to warm to room temperature over six hours, turning redat � 50 °C and black at � 30 °C. After separation of precipitate viafiltration, volatiles are evaporated under reduced pressure. Theremaining residue is washed with acetonitrile and 2 is obtained asa dark brown solid. Black crystals of 2 suitable for single crystal X-ray diffraction where grown from a mixture of toluene and diethylether at � 32 °C. Yield 94%. Elemental analysis for C48H68Bi2 calcd: C,54.23; H, 6.45; found: C, 54.12; H, 6.58; 1H NMR (300 MHz, C6D6) δ:7.08–7.21 (m, 12H, m-CH, p-CH), 3.23 (sept, 3JH-H=6.7 Hz, 8H,CH(CH3)2), 1.14 (d, 3JH-H=6.8 Hz, 24H, CH(CH3)2), 0.89 (d, 3JH-H=

6.8 Hz, 24H, CH(CH3)2);13C{1H} NMR (125 MHz, C6D6) δ: 156.3 (s, m-C),

128.9(s, p-C), 125.5 (s, o-C), 44.3 (s, CH(CH3)2), 25.7 (s, CH(CH3)2), 24.8(s, CH(CH3)2); IR (cm� 1): 3038 (w), 2952 (m), 2920 (w), 2861 (w), 1565(w), 1455 (w), 1381 (w), 1360 (w), 1291 (w), 1234 (w), 1174 (w), 1157(w), 1043 (w), 995 (w), 907 (w) 794 (s), 725 (s); HR-MS: CI(+) m/z531.2443 [0.5 M]+; calcd 531.2464

Reaction of 2 with elemental sulfur. Compound 2 (100 mg,0.09 mmol) is dissolved in 5 ml trifluortoluene and elemental sulfur(6 mg, 0.19 mmol) is added at room temperature. After stirring for90 minutes, volatiles are removed under reduced pressure and theremaining solid is extracted with 15 ml pentane. The solution isconcentrated and cooled to � 32 °C. Orange crystals of 3a and 3bwere obtained after one week.

Synthesis of Dipp2BiPtBu2 (4). a.) To a solution of compound 1-Br(150 mg, 0.24 mmol) in 10 ml of pentane, cooled to � 78 °C, LiPtBu2

(36.6 mg, 0.24 mmol) is added. The reaction mixture is allowed toreach 0 °C in the course of 5 hours under continuous stirring. Afterfiltration, all volatiles of the filtrate are removed under reducedpressure. The red compound 4 is obtained in crystalline form froma solution of the remaining solid in pentane at � 32 °C. Yield 32%.b.) Compound 1-F (100 mg, 0.18 mmol) was dissolved in 5 ml ofTFT, cooled to � 30 °C and 0.018 ml of PtBu2TMS (40 mg, 0.18 mmol)in 2 ml TFT are added. The solution was stirred for two days at� 30 °C. After removal of all volatiles under reduced pressure, theremaining solid is taken up in 0.5 ml pentane and compound 2 isobtained in the form of red crystals at � 32 °C. Yield 45%. Elemental

analysis for C32H52Bi1P1 calcd: C, 56.80; H, 7.75; found: C, 56.44; H,7.12; 1H NMR (300 MHz, C6D6) δ: 7.19–7.27 (m, 6H, m-CH), 3.57–3.74(m, 4H, p-CH), 1.38 (d, 3JP-H=10.6 Hz, 18H, P-C(CH3)3), 1.19 (d, 3JH-H=

6.6 Hz, 12H, CH(CH3)2), 1.12 (d, 3JH-H=6.6 Hz, 12H, CH(CH3)2);13C{1H}

NMR (125 MHz, C6D6) δ: 156.4 (s, m-C), 129.1 (s, p-C), 126.0 (s, o-C),41.1 (s, CH(CH3)2), 41.0 (s, CH(CH3)2), 35.4 (d, 1JP-C=44.0 Hz, P-C(CH3)3), 33.9 (d, 2JP-C=13.7 Hz, P-C(CH3)3), 25.4 (s, CH(CH3)2), 25.0 (s,CH(CH3)2);

31P{1H} NMR (122 MHz, C6D6) δ: 85.4 (s); IR (cm� 1): 3046(w), 2990(m), 2959 (m), 2928 (m), 2885 (m), 2858 (m), 1568 (w), 1459(m), 1445 (m), 1409 (w), 1382 (m), 1381(m), 1360 (m), 1308 (w), 1229(w), 1165 (w), 1148(w), 1044 (w), 1012 (w), 996 (w), 926 (w), 796 (s),724 (s), 592 (w), 557 (w), 492 (w), 462 (w), 424 (w); 145.1148 [M-Dipp2Bi]

+; calcd 145.1146

X-ray diffraction analysis. Single crystal X-ray diffraction analysiswas conducted using a Bruker D8 Quest and a Stoe IPDS 2diffractometer. The diffractometers use Mo� Kα (λ=0.71073 Å)radiation and respective X-ray optics. Structures were solved viaintrinsic phasing using SHELXT-2015. Structure refinement wasperformed via full-matrix-least-squares against F2 using SHELXL-2015. All structures were solved and refined using the OLEX2platform.65–68

Deposition Numbers 2012037 (1-F), 2012042 (1-Cl), 2012043 (1-Br),2012038 (1-I), 2012040 (1-OTf), 2012044 (2), 2012039 (3a), 2012041(3b), and 2032570 (4) contain the supplementary crystallographicdata for this paper. These data are provided free of charge by thejoint Cambridge Crystallographic Data Centre and Fachinforma-tionszentrum Karlsruhe Access Structures service www.ccdc.cam.a-c.uk/structures.

Acknowledgements

This work was financially supported by the Deutsche For-schungsgemeinschaft (DFG), GRK 1782 Functionalization of Semi-conductors. Open access funding enabled and organized byProjekt DEAL.

Conflict of Interest

The authors declare no conflict of interest.

Keywords: Bismuth · Halides · Interpnictogen compounds ·Organometallic chemistry · Sulfur activation

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Manuscript received: November 6, 2020Revised manuscript received: January 11, 2021Accepted manuscript online: January 13, 2021

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FULL PAPERS

All 2,6-diisopropylphenyl (Dipp) sub-stituted diaryl halido bismuthanesand diaryl triflato bismuthane wereprepared, fully characterized, andtheir crystal structures wereexamined. Functionalization withLiPtBu2 or tBu2PTMS gives access to

the interpnictogen compoundDipp2Bi� PtBu2. Moreover, the corre-sponding dibismuthane was preparedand its reactivity towards elementalsulfur was studied, yielding a dibismu-thanyl tri- and pentasulfane.

T. Dunaj, K. Dollberg, C. Ritter, Dr. F.Dankert, Prof. Dr. C. von Hänisch*

1 – 10

2,6-Diisopropylphenyl-SubstitutedBismuth Compounds: Synthesis,Structure, and Reactivity

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