TY - JOUR
T1 - The reductive activation of [M5C(CO)15] (M = Ru or Os) and subsequent reactions of the dianion [Os5C(CO) 14]2-, carbonylation of [M5C(CO)15] (M = Ru or Os), and the crystal structures of [Os5C(CO) 16], [N(PPh3)2]2[Os 5C(CO)14],...
AU - Johnson, Brian F.G.
AU - Lewis, Jack
AU - Nelson, William J.H.
AU - Nicholls, J. Nicola
AU - Puga, José
AU - Raithby, Paul R.
AU - Rosales, Maria J.
AU - Schröder, Martin
AU - Vargas, Maria D.
PY - 1983
Y1 - 1983
N2 - Title full:The reductive activation of [M5C(CO)15] (M = Ru or Os) and subsequent reactions of the dianion [Os5C(CO) 14]2-, carbonylation of [M5C(CO)15] (M = Ru or Os), and the crystal structures of [Os5C(CO) 16], [N(PPh3)2]2[Os 5C(CO)14], and [Os5C(CO) 14{Au(PPh3)}2]. High pressure infrared (h.p.i.r.) studies indicate that the cluster [Ru5C(CO)15] (1) adds carbon monoxide under relatively mild conditions (20 °C, 80 atm) to give [Ru5C(CO)16] (2), while under more forcing conditions (90 °C, 80 atm) the cluster (2) reverts back to (1). The osmium analogue, [Os5C(CO)15] (3), gives [Os5C(CO)16] (4) at 70 °C and 50 atm but may be obtained in quantitative yield from an autoclave reaction in the absence of solvent. Complex (4) crystallises in space group P1̄ with a = 10.017(3), b = 15.823(5), c = 16.507(8) Å, α = 96.78(3), β = 103.20(3), γ = 93.41(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier-difference techniques and refined by blocked full-matrix least squares to R = 0.073 for 6 120 reflections. The five Os atoms define a 'bridged-butterfly' configuration with a carbide at the centre. There are four terminal carbonyl groups bound to the bridging metal atom and three to each of the other four metal atoms. A h.p.i.r. study of the reaction of (4) with H2 has shown that at a pressure of 75 atm and at temperatures around 90 °C the cluster [Os5H2(C)(CO)15] (5) is produced. The electrochemical or chemical reduction of [M5C(CO) 15] [M = Ru (1) or Os (3)] produces the corresponding dianion [M 5C(CO)14]2- [M = Ru (6) or Os (7)]. An X-ray analysis of the [N(PPh3)2]+ salt of (7) shows that the squarepyramidal Os5C core geometry of (3) is retained. One of the Os-Os bonds in the basal plane is symmetrically bridged by a carbonyl group. The remaining 13 carbonyl ligands are co-ordinated terminally, two each to the carbonyl-bridged metal atoms, and three each to the other three metal atoms. The salt crystallises in space group P1̄ with a = 13.244(6), b = 14.648(9), c = 21.963(14) Å, α = 86.78(5), β = 85.54(5), γ = 81.22(5)°, and Z = 2. The structure was solved using the same techniques as for (4) and refined by blocked-cascade least squares to R = 0.065 for 5 780 observed diffractometer data. The dianion (7) reacts with two equivalents of [Au(PPh3)Cl] to give the neutral complex [Os 5C(CO)14{Au(PPh3)}2] (10) which has also been characterised crystallographically. In (10) the Os5C core shows significant distortions from square-pyramidal geometry. Two opposite Os(basal)-Os(apical) bonds are bridged by the Au atoms of the Au(PPh 3) ligands and these two bonds are significantly longer than the other two unbridged Os(basal)-Os(apical) bonds. Two carbonyl groups are bonded terminally to the apical Os atom, and three each to the four basal Os atoms. This complex crystallises in space group P21/c with a = 20.307(4), b = 9.843(2), c = 27.980(6) Å, β = 100.53(2)°, and Z = 4. The structure was solved and refined as for (7) to R = 0.060 for 7 013 observed diffractometer data.
AB - Title full:The reductive activation of [M5C(CO)15] (M = Ru or Os) and subsequent reactions of the dianion [Os5C(CO) 14]2-, carbonylation of [M5C(CO)15] (M = Ru or Os), and the crystal structures of [Os5C(CO) 16], [N(PPh3)2]2[Os 5C(CO)14], and [Os5C(CO) 14{Au(PPh3)}2]. High pressure infrared (h.p.i.r.) studies indicate that the cluster [Ru5C(CO)15] (1) adds carbon monoxide under relatively mild conditions (20 °C, 80 atm) to give [Ru5C(CO)16] (2), while under more forcing conditions (90 °C, 80 atm) the cluster (2) reverts back to (1). The osmium analogue, [Os5C(CO)15] (3), gives [Os5C(CO)16] (4) at 70 °C and 50 atm but may be obtained in quantitative yield from an autoclave reaction in the absence of solvent. Complex (4) crystallises in space group P1̄ with a = 10.017(3), b = 15.823(5), c = 16.507(8) Å, α = 96.78(3), β = 103.20(3), γ = 93.41(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier-difference techniques and refined by blocked full-matrix least squares to R = 0.073 for 6 120 reflections. The five Os atoms define a 'bridged-butterfly' configuration with a carbide at the centre. There are four terminal carbonyl groups bound to the bridging metal atom and three to each of the other four metal atoms. A h.p.i.r. study of the reaction of (4) with H2 has shown that at a pressure of 75 atm and at temperatures around 90 °C the cluster [Os5H2(C)(CO)15] (5) is produced. The electrochemical or chemical reduction of [M5C(CO) 15] [M = Ru (1) or Os (3)] produces the corresponding dianion [M 5C(CO)14]2- [M = Ru (6) or Os (7)]. An X-ray analysis of the [N(PPh3)2]+ salt of (7) shows that the squarepyramidal Os5C core geometry of (3) is retained. One of the Os-Os bonds in the basal plane is symmetrically bridged by a carbonyl group. The remaining 13 carbonyl ligands are co-ordinated terminally, two each to the carbonyl-bridged metal atoms, and three each to the other three metal atoms. The salt crystallises in space group P1̄ with a = 13.244(6), b = 14.648(9), c = 21.963(14) Å, α = 86.78(5), β = 85.54(5), γ = 81.22(5)°, and Z = 2. The structure was solved using the same techniques as for (4) and refined by blocked-cascade least squares to R = 0.065 for 5 780 observed diffractometer data. The dianion (7) reacts with two equivalents of [Au(PPh3)Cl] to give the neutral complex [Os 5C(CO)14{Au(PPh3)}2] (10) which has also been characterised crystallographically. In (10) the Os5C core shows significant distortions from square-pyramidal geometry. Two opposite Os(basal)-Os(apical) bonds are bridged by the Au atoms of the Au(PPh 3) ligands and these two bonds are significantly longer than the other two unbridged Os(basal)-Os(apical) bonds. Two carbonyl groups are bonded terminally to the apical Os atom, and three each to the four basal Os atoms. This complex crystallises in space group P21/c with a = 20.307(4), b = 9.843(2), c = 27.980(6) Å, β = 100.53(2)°, and Z = 4. The structure was solved and refined as for (7) to R = 0.060 for 7 013 observed diffractometer data.
UR - https://www.scopus.com/pages/publications/51149219760
U2 - 10.1039/DT9830002447
DO - 10.1039/DT9830002447
M3 - Article
AN - SCOPUS:51149219760
SN - 1472-7773
SP - 2447
EP - 2457
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 11
ER -