Control of Si–C bond cleavage at carbon α to phosphorus. Suppression of facile protodesilylation of PPh₂CH₂SiMe₂H by complexation through phosphorus to ruthenium and the X-ray crystal and molecular structure of [Ru(η⁶-p-cymene)Cl₂(PPh₂CH₂SiMe₂OH)]

Abstract

Facile cleavage of the Si-C bond a t o P in Ph2PCH2SiMe2H which is induced by HY (Y = OH, OMe, or CI) is suppressed on complexation at Ru in [Ru(q6-cym)CI2( PPh2CH2SiMe2H)] (cym = p-cymene); instead the latter reacts where Y = OH t o afford the silanol complex [Ru(q6-cym)CI2(PPh2CH2SiMe2OH)] which has been structurally characterized by X-ray diffraction.

Synthesis, X-ray structure, and nuclear magnetic resonance (1H and 13C) studies of ruthenium(II) complexes containing pyrazolyl ligands

“…measurements revealed that complex (9) was obtained as a mixture of isomers (9a) and (9b) in variable relative proportions (see above). Complexes (6)-- (8) were obtained by the same method.…”

Complexes of Ruthenium and Osmium Containing η2–η6 Hydrocarbon Ligands: (iii) Complexes Containing Six-, Seven- and Eight-membered Rings

“…112 Slow crystallization from wet acetone of a mixture of [{RuCl 2 (T|-cym)} 2 ] and Ph 2 PCH 2 SiMe 2 H gives the phosphino-silanol complex [RuCl 2 (PPh 2 CH 2 SiMe 2 OH)(r|-cym)]*, whereas free Ph 2 PCH 2 SiMe 2 H is rapidly cleaved by protic agents to Ph 2 PMe. 113 The diastereomers formed by reaction of (+)-neomenthyldiphenylphosphine with [{RuCl 2 (r|-o-MeC 6 H 4 CO 2 Me)}2] can be separated by fractional crystallization; the less soluble diastereomer has the (R) configuration at the chiral planar unit. The separated diastereomers are converted into the enantiomeric (R,R) and (S,S) forms o f [ { R u C l 2 ( r j -6 > -MeC 6 H 4 CO 2 Me)} 2 ] by heating with cod in propan-2-ol and subsequent treatment of the cod complexes with HC1.…”

The X-ray structure of a protonated hypervalent silanol

“…Solid state silanol structures which do not involve any hydrogen bonding are known but are comparatively rare. 7 Thus, intermolecular hydrogen bonding in silanols has been extensively studied and shown to take many forms. 8 For example, diisopropylsilanediol, 9 exists as hydrogen bonded dimers which are linked together in ladder chains by further hydrogen bonds, and tris(trimethylsilyl)silylsilanetriol 10 forms hexameric cages of hydrogen bonds.…”