New complexes with MSiO or MSiS linkages (M=Fe or Co)

Abstract

Ph 2 XSiFe(CO) 2 Cp [X = p-tolylS (1a), MeO (1b)] and Ph[2-MeOC 6 H 4 ]XSiFe(CO) 2 Cp [X = Cl (2a), OMe (2b)] have been fully characterised, including X-ray crystal structure determinations for 1a, 1b and 2a. None of the examples showed any tendency for migration of the X groups from silicon to iron, with elimination of silylene. However very ready loss of the X groups was seen in the electrospray mass spectra, suggesting formation of the cationic silylene-iron complex ions is favoured. This was especially so for 2a and 2b, where intramolecular stabilisation of the silicon centre from the 2-OMe group is possible.The stable siloxane O[SiPh 2 {Co(CO) 4 }] 2 was also characterised; the X-ray crystal structure analysis shows a Si-O-Si bond angle of 153°.

Tethered silyl complexes from nucleophilic substitution reactions at the Si–Cl bond of the chloro(diphenyl)silyl ligand in Ru(SiClPh2)(κ2-S2CNMe2)(CO)(PPh3)2

“…for C 52 H 46 ClNOP 2 RuS 2 Si: C,62.99;H,4.68;N,1.41. Found: C,62.78;H,4.71 Ru(SiPh 2 Cl)(j 2 -S 2 CNMe 2 )(CO)(PPh 3 ) 2 (173.5 mg, 0.175 mmol) and 2-hydroxypyridine (33.3 mg, 0.35 mmol) were added to benzene (20 ml) under nitrogen. The white suspension was stirred for 1 h and then filtered through Celite.…”

“…for C 39 H 35 N 2 O 2 PRuS 2Si: C, 58.82;H, 4.55; N, 3.61. Found: C, 58.58;H, 4.38; N, 3.43%. IR (cm À1 ): 1915 m(CO).…”

Recent chemistry of the η5-cyclopentadienyl dicarbonyl iron anion

“…McIndoe and Nicholson prepared [166] Fp silane complexes (Scheme 103) to characterize and study their structural relationship and tendency to undergo 1,2-migration of the X-containing aryl group from silicon to the iron center. There was no tendency for the X-group on silicon to migrate to iron, thus elimination of silylene was not observed.…”

Broadening the Scope of Ancillary Phosphane‐Type Ligands: A Systematic Comparison of PR3, PR2BH3–, and SiR3– and Their Chalcogen Derivatives

“…Nevertheless, there are a number of silyl complexes with known molecular structures where the silicon atom is bound to electron-withdrawing functional groups. [50][51][52][53] Complexes of Fp + bearing silyl ligands with solely aryl and/or alkyl substituents have, however, been spectroscopically characterized and are typically obtained by treating NaFp with a triorganylsilyl chloride. [54][55][56][57] The σ-donor properties of the phosphanyl borohydride 2a (Figure 2) towards selected main group Lewis acids have already been explored.…”