TY - JOUR
T1 - Synthesis of mixed-metal clusters by the reaction of the unsaturated cluster [Os3(μ-H)2(CO)10] with transition-metal hydrides
T2 - The X-ray crystal structures of [Os3H3(CO)10{Cu(PPh3)}] and [Os3H3(CO)11{Ir(PPh3)}]
AU - Johnson, Brian F. G.
AU - Lewis, Jack
AU - Raithby, Paul R.
AU - Azman, S. N.
AU - Syed-Mustaffa, B.
AU - Taylor, Michael J.
AU - Whitmire, Kenton H.
AU - Clegg, William
PY - 1984/12/31
Y1 - 1984/12/31
N2 - The co-ordinatively unsaturated dihydride cluster [Os3(μ-H)2(CO)10] reacts with the transition-metal hydrides [{CuH(PPh3)}6], [IrH(CO)2(PPh3)2], [RhH(CO)(PPh3)2], and [NiH(Cl)({P(C6H11)3}2] to give the mixed-metal clusters [Os3H3(CO)10{Cu(PPh3)}] (1), [Os3H3(CO)11{Ir(PPh3)}] (2), [Os3H3(CO)11{Rh(PPh3)}] (3), and [Os3H2(CO)10{Ni[P(C6H 11)3]}] (4). These complexes have been characterized by i.r. and n.m.r. spectroscopy, and the structures of (1) and (2) have been established by single-crystal X-ray analysis. In complex (1) the three Os atoms lie at the vertices of an isosceles triangle the long edge [3.026(3) Å] of which is bridged by the Cu atom of the Cu(PPh3) ligand. The hydrides were not located directly but evidence suggests that they bridge the long Os-Os bond and the two Os-Cu bonds. The carbonyl arrangement is similar to that observed in [Os3H2(CO)10]. In complex (2) the Ir atom caps the Os3 triangle to form a distorted tetrahedral metal framework. The three Ir-Os bond lengths [2.759(3), 2.789(2), and 2.917(3) Å] show considerable variation. The distribution of the eleven terminal carbonyl ligands and the phosphine group, which is co-ordinated to the Ir atom, indicates that the three hydrides bridge the two longer Os-Os bonds, and the longest Os-Ir bond. From the spectroscopic data the overall geometry of complex (3) is closely related to that of (2), while (4) has a tetrahedral metal arrangement with hydrides and carbonyl groups bridging Os-Os and Os-Ni edges.
AB - The co-ordinatively unsaturated dihydride cluster [Os3(μ-H)2(CO)10] reacts with the transition-metal hydrides [{CuH(PPh3)}6], [IrH(CO)2(PPh3)2], [RhH(CO)(PPh3)2], and [NiH(Cl)({P(C6H11)3}2] to give the mixed-metal clusters [Os3H3(CO)10{Cu(PPh3)}] (1), [Os3H3(CO)11{Ir(PPh3)}] (2), [Os3H3(CO)11{Rh(PPh3)}] (3), and [Os3H2(CO)10{Ni[P(C6H 11)3]}] (4). These complexes have been characterized by i.r. and n.m.r. spectroscopy, and the structures of (1) and (2) have been established by single-crystal X-ray analysis. In complex (1) the three Os atoms lie at the vertices of an isosceles triangle the long edge [3.026(3) Å] of which is bridged by the Cu atom of the Cu(PPh3) ligand. The hydrides were not located directly but evidence suggests that they bridge the long Os-Os bond and the two Os-Cu bonds. The carbonyl arrangement is similar to that observed in [Os3H2(CO)10]. In complex (2) the Ir atom caps the Os3 triangle to form a distorted tetrahedral metal framework. The three Ir-Os bond lengths [2.759(3), 2.789(2), and 2.917(3) Å] show considerable variation. The distribution of the eleven terminal carbonyl ligands and the phosphine group, which is co-ordinated to the Ir atom, indicates that the three hydrides bridge the two longer Os-Os bonds, and the longest Os-Ir bond. From the spectroscopic data the overall geometry of complex (3) is closely related to that of (2), while (4) has a tetrahedral metal arrangement with hydrides and carbonyl groups bridging Os-Os and Os-Ni edges.
UR - http://www.scopus.com/inward/record.url?scp=37049095793&partnerID=8YFLogxK
U2 - 10.1039/DT9840002111
DO - 10.1039/DT9840002111
M3 - Article
AN - SCOPUS:37049095793
SN - 1472-7773
SP - 2111
EP - 2118
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 10
ER -