ISSN:
0009-2940
Keywords:
Stannyl complexes
;
Hydride complexes
;
Three-center bonds
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Transition-Metal Stannyl Complexes, 3. - Metal, Hydrogen, Tin Three-Center Bonding in Group VI Hydrido Stannyl ComplexesThe hydrido stannyl complex (π-1,3,5-Me3C6H3)(CO)2Cr(H)-SnPh3 (1) is prepared by photochemical reaction of (π-1,3,5-Me3C6H3)(CO)3Cr with HSnPh3. The 119SnHCr coupling constant (327.6 Hz) and an X-ray structure analysis [Sn - H 202(4), Cr - H 159(4), Cr - Sn 270.16(6) pm] show that the Sn - H bond is coordinated in an η2 fashion. The complexes (CO)4(R3P)-W(H)SnPh3 (R3P=Ph3P, MePh2P) (2) and (CO)3(dppe)M(H)-SnR3 (M=Cr, SnR3=SnPh3; M=Mo, SnR3=SnMe3, SnPh3; M=W, SnR3=SnMe3, SnPh2Me, SnPh3) (4 - 6) are obtained either by thermal reaction of (CO)4(R3P)W(THF) or (CO)3(dppe)ML (L=THF, acetone) with HSiR3, or by photochemical reaction of (CO)4(dppe)M with HSnPh3. Reaction of (CO)4(Ph3P)W(THF) with HSnMe3 yields (CO)4(Ph3P)W(Sn-Me3)2 (3). The Sn,M,H coupling constants in the complexes 2 and (CO)3(dppe)M(H)SnR3 (M=Cr, Mo) are in the range of 250 - 315 Hz and therefore these complexes seem to contain an η2-coordinated stannane. Contrary to this, the SnWH coupling constants in (CO)3(dppe)W(H)SnR3 are considerably lower (70 - 90 Hz), suggesting complete oxidative addition of the H - Sn bond. The complexes (CO)3(dppe)M(H)SnPh3 decompose in benzene solution at room temperature to give, inter alia, hexaphenyldistannane. Ph6Sn2 · 2 C6H6 crystallizes in the space group \documentclass{article}\pagestyle{empty}\begin{document}$ R\bar 3 $\end{document} (Z=1); in the crystal lattice the benzene molecules are perpendicular to the three-fold axis of symmetry of the distannane molecule.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240411
