Tin(iv) halide complexes of AsPh₃: The structures of trans-SnCl₄(AsPh₃)₂and SnBr₄(AsPh₃)·AsPh₃

Abstract

The structures of two 1 : 2 adducts between tin(IV) halides and AsPh(3) have been determined. SnCl(4)(AsPh(3))(2) adopts a six-coordinate geometry at tin in which the two organoarsine donors are mutually trans. In contrast, SnBr(4)(AsPh(3))(2) is five-coordinate at tin and only one arsine is directly bonded to the metal, in an axial site of the trigonal bipyramid. The second AsPh(3) group has a close contact with the axially bound bromine [As...Br: 3.567(3) angstroms], which is a unique structural variation that depicts an intermediate in a halogen-transfer reaction between Group 14 and Group 15 elements. AACVD using SnCl(4)(AsPh(3))(2) generates a film containing SnO(2) and a second crystalline material which is possibly SnCl(2), but which contains no arsenic.

Atmospheric Pressure Chemical Vapour Deposition of TiCl4 and tBuAsH2 to Form Titanium Arsenide Thin Films

“…[24] Apart from CoAs, [25] MnAs, [26] and the key III/V materials (AlAs, GaAs and InAs), knowledge of metal arsenide thin film remains limited. [27] However, metal arsenides have been studied in their solid forms, where traditionally they have been formed by solid state metathesis reactions. [28][29][30] Following the previous results observed with the replacement of PH 3 by tBuPH 2 , [12] similar studies were carried out to seek potential AsH 3 alternatives.…”

Coordination chemistry of the main group elements with phosphine, arsine and stibine ligands

“…For tertiary phosphines the six-coordinate trans-[SnX 4 (PR 3 ) 2 ] are the usual solid products, exemplified by those of PMe 3 [284,287], PEt 3 [282], PPh 3 , PMe 2 Ph and P n Bu 3 [292], although NMR spectroscopy often identifies a mixture of cis and trans isomers in solution. AsPh 3 complexes of both 1:1 and 2:1 stoichiometry have been reported [285,294]. Interestingly, Mahon et al [285] determined the X-ray structures of [SnX 4 (AsPh 3 ) 2 ], finding that the chloride was the expected six-coordinate trans isomer (Fig.…”

“…AsPh 3 complexes of both 1:1 and 2:1 stoichiometry have been reported [285,294]. Interestingly, Mahon et al [285] determined the X-ray structures of [SnX 4 (AsPh 3 ) 2 ], finding that the chloride was the expected six-coordinate trans isomer (Fig. 49), but the bromide was trigonal bipyramidal [SnBr 4 (AsPh 3 )] with a second uncoordinated AsPh 3 group in the lattice interacting with the axial Br group (Fig.…”

“…The quality/purity of the deposits is critical to their use in electronic devices and minimal carbon or halogen contamination is very important. Detailed descriptions of the application of Group 13 adducts are in the reviews cited, but examples are the preparation of nanocrystalline GaP from thermolysis of [GaX 3 {P(SiMe 3 ) 3 }] (X = Cl, Br or I) [178], and similarly of InP and InAs from [InX 3 {E(SiMe 3 ) 3 }] (E = P or As) [225] Attempts to deposit GeP by AACVD from [GeCl 3 (PCyH)] produced films containing GeP but these had a very high oxygen content [271], whilst similar use of [SnCl 4 (AsPh 3 ) 2 ] produced arsenic-free deposits of SnO 2 [285]. Nevertheless these two unsuccessful attempts do not invalidate the idea of utilising this type of complex for the deposition of elements or alloys outside of Ga or In work.…”

“…[281,282,[285][286][287]292]. For tertiary phosphines the six-coordinate trans-[SnX 4 (PR 3 ) 2 ] are the usual solid products, exemplified by those of PMe 3 [284,287], PEt 3 [282], PPh 3 , PMe 2 Ph and P n Bu 3 [292], although NMR spectroscopy often identifies a mixture of cis and trans isomers in solution.…”