“…Complexes 1 , 2 , and 5 adopt a three-legged “piano-stool” geometry around ruthenium, with “legs” composed of one PPh 3 and two silyl groups. The Ru−Si distances of 2.32−2.44 Å are consistent with a single bond and fall within the range (2.27−2.51 Å) observed for d 6 ruthenium silyl complexes. ,,,,, Also, in these complexes, the average Si−Cl distance (2.10 ± 0.01 Å) was slightly longer than the Si−Cl distances in (η 6 - p -Bu t 2 C 6 H 4 )Ru(CO)(SiCl 3 ) 2 (2.07 ± 0.01 Å) but shorter than the Si−Cl distances (2.11−2.17, 2.13 ± 0.01 Å average) observed in related d 6 Cp(PR 3 ) 2 Ru(SiX 3 ) complexes. ,, 2 Perspective view of the molecular structure of (η 6 -C 6 H 6 )Ru(PPh 3 )(SiCl 3 ) 2 ( 1 ) with atom labels provided for all unique non-hydrogen atoms. The thermal ellipsoids are scaled to enclose 30% probability. 3 Perspective view of the molecular structure of (η 6 -C 6 H 6 )Ru(PPh 3 )(SiMeCl 2 ) 2 ( 2 ) with atom labels provided for all unique non-hydrogen atoms.…”
The reaction of RuCl2(PPh3)3 with HSiX3 in benzene produced (η6-benzene)Ru(PPh3)(SiX3)2
(SiX3 = SiCl3 (1), SiMeCl2 (2)) as white to light yellow solids in high yields (>80%). A mixture
of (η6-benzene)Ru(PPh3)(SiMe2Cl)2 (3), (η6-benzene)Ru(PPh3)(SiMe2Cl)(SiMeCl2) (4), and 2,
due to silicon substituent redistribution, was obtained from the reaction of RuCl2(PPh3)3
with HSiMe2Cl in benzene. (η6-benzene)Ru(PPh3)(SiMe3)2 (5) was prepared by the methylation of 1, 2, or the 3/4 mixture with AlMe3. The related complexes (η6-arene)Ru(PPh3)(SiMeCl2)2 (arene = toluene (6), o-xylene (7), m-xylene (8), p-xylene (9), mesitylene (10),
anisole (11)) were obtained from the reaction of RuCl2(PPh3)3 with HSiMeCl2 in the
corresponding arene solvent at elevated temperature. Complexes 1, 2, and 5 were structurally
characterized by single-crystal X-ray diffraction and exhibit a characteristic three-legged
“piano-stool” geometry. The Ru−Si distances, in these complexes, ranged from 2.322 to 2.438
Å; the Ru−Si distance increased as the number of methyl groups on silicon increased.
“…Complexes 1 , 2 , and 5 adopt a three-legged “piano-stool” geometry around ruthenium, with “legs” composed of one PPh 3 and two silyl groups. The Ru−Si distances of 2.32−2.44 Å are consistent with a single bond and fall within the range (2.27−2.51 Å) observed for d 6 ruthenium silyl complexes. ,,,,, Also, in these complexes, the average Si−Cl distance (2.10 ± 0.01 Å) was slightly longer than the Si−Cl distances in (η 6 - p -Bu t 2 C 6 H 4 )Ru(CO)(SiCl 3 ) 2 (2.07 ± 0.01 Å) but shorter than the Si−Cl distances (2.11−2.17, 2.13 ± 0.01 Å average) observed in related d 6 Cp(PR 3 ) 2 Ru(SiX 3 ) complexes. ,, 2 Perspective view of the molecular structure of (η 6 -C 6 H 6 )Ru(PPh 3 )(SiCl 3 ) 2 ( 1 ) with atom labels provided for all unique non-hydrogen atoms. The thermal ellipsoids are scaled to enclose 30% probability. 3 Perspective view of the molecular structure of (η 6 -C 6 H 6 )Ru(PPh 3 )(SiMeCl 2 ) 2 ( 2 ) with atom labels provided for all unique non-hydrogen atoms.…”
The reaction of RuCl2(PPh3)3 with HSiX3 in benzene produced (η6-benzene)Ru(PPh3)(SiX3)2
(SiX3 = SiCl3 (1), SiMeCl2 (2)) as white to light yellow solids in high yields (>80%). A mixture
of (η6-benzene)Ru(PPh3)(SiMe2Cl)2 (3), (η6-benzene)Ru(PPh3)(SiMe2Cl)(SiMeCl2) (4), and 2,
due to silicon substituent redistribution, was obtained from the reaction of RuCl2(PPh3)3
with HSiMe2Cl in benzene. (η6-benzene)Ru(PPh3)(SiMe3)2 (5) was prepared by the methylation of 1, 2, or the 3/4 mixture with AlMe3. The related complexes (η6-arene)Ru(PPh3)(SiMeCl2)2 (arene = toluene (6), o-xylene (7), m-xylene (8), p-xylene (9), mesitylene (10),
anisole (11)) were obtained from the reaction of RuCl2(PPh3)3 with HSiMeCl2 in the
corresponding arene solvent at elevated temperature. Complexes 1, 2, and 5 were structurally
characterized by single-crystal X-ray diffraction and exhibit a characteristic three-legged
“piano-stool” geometry. The Ru−Si distances, in these complexes, ranged from 2.322 to 2.438
Å; the Ru−Si distance increased as the number of methyl groups on silicon increased.
“…This is close to typical shifts for tetrasilyl substituted disilenes, which range from +140 to +155 ppm. Chemical shifts for the coordinated silicon atom of the isotetrasilanyl unit of mono- or disilylated , hafno- and zirconocenes lie in the range of −50 to −100 ppm. For known ethylene titanocene complexes, 13 C NMR spectra show a similar upfield shift of some 20 ppm for the coordinated ethylene resonances compared to free ethylene.…”
Reaction of the magnesium transmetalation product of a 1,2-dipotassiodisilane with hafnocene dichloride gives a disilene hafnocene complex. X-ray crystallography of the respective trimethylphosphane adduct provides structural proof for this assignment.
“…For a d 0 Ta(V) center, donation from a ligand-based orbital into the π * orbital of the CO ligand could lead to a stable complex , of d 2 Ta(III) and d → π * back-bonding to the CO ligand. The observed J Si(Ta)H coupling constant of 28.5 Hz is intermediate between ranges expected for predominant η 2 -silane character (50−80 Hz) and classical silyl hydrides (≤20 Hz),12a but is virtually identical to the corresponding value of 28 Hz reported for Cp 2 Ti(H)(SiHPh 2 )(PMe 3 ), which was shown to have considerable η 2 -silane character 3b.…”
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