Stibines structure

The octet rule similarly retains some significance for third-row atoms and still heavier atoms, aside from those of the transition elements. Thus we can, for example, assign to arsine and stibine structures analogous to those for phosphine, using the four av.d p orbitals of the valence shell of the central atom. 

Considerable structural information is available on osmium complexes of tertiary phosphines, arsines and stibines (Table 1.13) [152, 157]. 

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. 

Considerable structural information is available on osmium complexes of tertiary phosphines, arsines and stibines (Table 1.13) [152, 157], Comparison with data (mainly obtained from EXAFS measurements) on osmium diarsine complexes (Table 1.14) shows that as the oxidation state increases, osmium-halogen bonds shorten whereas Os-P and Os-As bonds lengthen. Bond shortening is predicted for bonds with ionic character,... 

From a structural point of view the complexes with tertiary stibine ligands are very uniform. The predominant type is rj coordination (type 1), with electron pair donation of the Sb atom to the metal centre.1,2,6,8 However, complexes with bridging stibine ligands (type 2) are also known.13,14 (Scheme 1). 

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. 

Stibinoalanes, 262-264, 266-268, 269 for AlSb film deposition, 301-303 see also Alane stibine adducts Stibinogallanes, 261-262, 269-272, 294-295 in film deposition, 303 Stibinoindanes, 261-262, 264, 272, 273 in film deposition, 303-304 Structure... 

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