Stibine crystal structure

Related to tertiary stibines is the (Me3Si)3Sb ligand. Recent studies of this ligand comprise coordination on transition metal and main group element centers. An example for a transition metal complex with a known crystal structure is [(CO)5CrSb(SiMe3)3],5° the structure of which is depicted in Fig. 2. 

Phenylstibine [58266-50-5], C H Sb, has been obtained by the reduction of phenyldiiodostibine [68972-61 -2], C6HBI2Sb, (73) or phenyldichlorostibine [5035-52-9], CH Q Sb, (74) with lithium borohydride. It has also been prepared by the hydrolysis or methanolysis of phenylbis(trimethylsilyl)stibine [82363-95-9], C H S Sb (75). Diphenylstibine [5865-81-6], C12HnSb, can be prepared by the interaction of diphenylchlorostibine [2629-47-2], C12H10QSb, with either lithium borohydride (76) or lithium aluminum hydride (77). It is also formed by hydrolysis or methanolysis of diphenyl(trimethylsilyl)stibine [69561-88-2], C15H19SbSi (75). Dimesitylstibine [121810-02-4] has been obtained by the protonation of lithium dimesitylstibide with trimethylammonium chloride (78). The x-ray crystal structure of this secondary stibine has also been reported... 

Wells et al. characterized group 13-stibine adducts by single crystal X-ray structure analyses first in 1997 [35]. The solid state structures of three borane-stibine adducts of the type X3B—Sb(Tms)3 (X = Cl 6, Br 7, I 8), obtained by reaction of boron trihalides BX3 and Sb(Tms)3 in n-pentane, were determined. 

Reliable information on the thermodynamic stability of group 13/15 adducts is usually obtained by gas phase measurements. However, due to the lability of stibine and bismuthine adducts in the gas phase toward dissociation, temperature-dependent H-NMR studies are also useful for the determination of their dissociation enthalpies in solution [41b], We focussed on analogously substituted adducts t-BusAl—E(f-Pr)3 (E = P 9, As 10, Sb 11, Bi 12) since they have been fully characterized by single crystal X-ray diffraction, allowing comparisons of their thermodynamic stability in solution with structural trends as found in their solid state structures. 

Up to now, fifteen group 13-stibine R3AI—SbR and four group 13-bismuthine adducts R3AI—BiR3 have been structurally characterized by single crystal X-ray diffraction studies. Their central structural parameters are summarized in Table 5. Structures 1-4 show the solid state structures of four representative adducts. 

The single crystal X-ray structure of fra .y-[Ru(bipy)2(PPh3)2]2+1122,1123 and the synthesis of related bis(phosphine) complexes1005 have been reported. Reaction of [RuCljL ] (L = bipy,1124, 2-(aryl-azo)pyridine1066) with phosphine, arsine and stibine ligands (I/) affords the complexes [RuC1(L)2L ]+ while with bidentate ligands L [Ru(bipy)2L ]2+ can be isolated.1124 (See Section 45.5). 

Numerous phosphine complexes (and some arsine and stibine analogues) are known. With monophosphines these are mainly of the type (R3P) AgX, with rt = 1-4. The 1 1 complexes are tetrameric, with either cubane (18-I-II) or chair (18-I-III) structures depending on the steric requirements of both X and R3P Ag4I4(PPh3)4 undergoes cube-chair isomerization, and the two structural types may be obtained by crystallization from different solvents. 

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