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Transition-Metal-Silyl Complexes, 20. - Investigations on the Reactivity of the Anionic Silyl Complexes -
Schubert, Ulrich,Kunz, Erika,Knorr, Michael,Mueller, Johannes
, p. 1079 - 1086 (2007/10/02)
Phosphane-substituted anionic silyl complexes - (1) are distinctly more reactive than their tetracarbonyl analoga, particularly towards metal or metal-complex halides.Their solution structure depends on the corresponding cation, with which they are able to form contact ion pairs.Reaction of 1 with CH3I, Me2SiHCl or Me3SnCl (R''3EX) yields phosphanesubstituted alkyl silyl, bissilyl or silyl stannyl complexes mer-Fe(CO)3(PR'3)(ER''3)SiR3.By reaction of 1 with (Ph3PAgCl)4, Ph3PAuCl, PhHgBr, or HgBr2 (LnMX) stable hetero-binuclear complexes mer-Fe(CO)3(PR'3)(SiR3)MLn can be prepared, which contain unsupported Fe-Ag-, Fe-Au-, or Fe-Hg bonds.X-ray structure analysis of Fe(CO)3(PPh3)(SiMePh2)AuPPh3 (6) (Fe-Au 255.1 (1), Fe-Si 235.7 (3) pm) reveals that the SiMePh2 and the PPh3 ligand are cis oriented to the Fe-Au bond.
