The structurally characterised silyl complexes, Os(κ2-S2CNMe2)(SiMeCl2)(CO)(PPh3)2 and Os(κ2-S2CNMe2)(SiCl3)(CO)(PPh3)2, which have remarkably unreactive Si–Cl bonds

Similarities and Contrasts between Silyl and Stannyl Derivatives of Ruthenium and Osmium

“…A plausible interpretation is that the facile hydrolysis of coordinatively unsaturated Os(SiCl 3 )Cl(CO)(PPh 3 ) 2 occurs because the nucleophile, hydroxide, attacks at the osmium to form an anionic complex, [Os(SiCl 3 )Cl(OH)(CO)(PPh 3 ) 2 ] - , and the ensuing hydrolysis becomes intramolecular. Support for this anionic intermediate is that the closely related anion [Os(SiCl 3 )Cl 2 (CO)(PPh 3 ) 2 ] - has been characterized . This same contrast in reactivity toward hydroxide is also shown by the two chlorodimethylsilyl complexes Os(SiMe 2 Cl)Cl(CO)(PPh 3 ) 2 and Os(SiMe 2 Cl)(κ 2 -S 2 CNMe 2 )(CO)(PPh 3 ) 2 ; the first of these two is readily hydrolyzed, but the six-coordinate complex is not …”

“…In striking contrast to the facile hydrolysis of Os(SiCl 3 )Cl(CO)(PPh 3 ) 2 , the coordinatively saturated trichlorosilyl complex Os(SiCl 3 )(κ 2 -S 2 CNMe 2 )(CO)(PPh 3 ) 2 ( 52 ) is completely resistant to hydrolysis, even under very forcing conditions (see Scheme ) . It is difficult to believe that the steric environment about the silicon differs significantly in these two compounds, and the dramatic difference in reactivity must be because a different mechanism of hydrolysis is available to the coordinatively unsaturated complex 23 .…”

Reactions of Hydrosilanes with Transition Metal Complexes and Characterization of the Products

“… 53 Table 1, footnote 54 22 54 SiH data taken from ref 206 . 55 Table 3, footnote 169 223 56 Fe−Si : 2.196; 372 2.199(2); 2.204(3); 2.204(3); 2.204(3); 2.206(3); 2.2064(9); 2.2099; 2.2225(9); 2.2227(13); 374 2.2239(7); 2.2318; 2.2320(1); 2.243(4); 376c 2.2466; 2.249(4); 376c 2.261(4); 2.262(1); 2.263(1); 2.263(2); 2.263(2); 2.2640(10); 2.265(1); 90 7(4); 2.2689(5); 46 2.2698(2); 2.2722(9); 2.272(7); 2.272(4); 2.274(2); 2.274(2); 2.275(2); 2.280(1); 90 2.2811(11); 380 2.285(3); 2.285(2); 385 2.289(2); 2.290(10); 2.290(2); 2.291(4); 2.2914(13); 2.292(1); 2.2924(4); 2.293(3); 2.294(2); 380 2.2944(8); 2.2947(5); 2.2955(4); 2.296(1); 2.296(1); 2.296(2); 2.298(2); 2.2980(9); 2.2982(8); 2.2990; 2.2992(16); 2.3010(6); 2.3021(19); 2.3021(19); 2.303(1); 2.303(2); 2.303(5) (disorder); 2.304; 384 2.3048(3); 2.3048(3); 2.305(2); 385 2.306(2); 2.307(2); 2.308; 2.308; 2.309(10); 2.3091(5); 2.3093(8); 385 2.3093(10);…”

“…Two examples illustrated here show how the effect of changing the number of Cl substitutents at Si does not cause dramatic changes. For the complex, Cp(Me 3 P)(ArN)HTa−SiMe x Cl 3− x , the difference for the Ta−Si bond distance for x = 1 ( 3-26a ) and x = 2 ( 3-25a ) is only 0.005 Å, ,,, and for (OC)(Ph 3 P)(Me 2 NCS 2 )OsSiMe x Cl 3− x [ x = 0 ( 3-154 ) and x = 1 (Table , footnote 169)] the difference is 0.022 Å . Ligands at the metal may not influence the TM−Si bond distance significantly, as is illustrated in the two Rh complexes (Ph 3 P) 2 (X)HRhSi(OEt) 3 ( 3-205 , X = Cl, and 3-206 , X = I) that have identical Rh−Si distances .…”

“… 168 Additional derivative, R = Ph 169 Additional derivative prepared from (OC)(Ph 3 P) 2 (Me 2 NCS 2 )OsH + HSiMeCl 2 170 Additional derivative, (OC)(Ph 3 P) 2 ClOsSi{OCH 2 CH 2 } 3 N …”