TY - JOUR
T1 - Synthesis of the anion [Ru3H(μ3-PPh)(CO)9]- and its reactions with complexes of Re, Rh, Ir, Cu, Ag, and Au to give heterometallic clusters containing a triruthenium unit
T2 - Crystal structures of the complexes [Ru3Rh2(μ4-PPh)(CO)13(PEt 3)] and...
AU - Mays, Martin J.
AU - Raithby, Paul R.
AU - Taylor, Philip L.
AU - Henrick, Kim
PY - 1984/7/14
Y1 - 1984/7/14
N2 - full title: Synthesis of the anion [Ru3H(μ3-PPh)(CO)9]- and its reactions with complexes of Re, Rh, Ir, Cu, Ag, and Au to give heterometallic clusters containing a triruthenium unit: Crystal structures of the complexes [Ru3Rh2(μ4-PPh)(CO)13(PEt 3)] and [Ru3{μ-Au(PMe2Ph)}(μ-H)(μ 3-PPh)(CO)9] Deprotonation of [Ru3H2(μ3-PPh)(CO)9] with base gives the anion [Ru3H(μ3-PPh)(CO)9]- which has been isolated as its [N(PPh3)2] + salt. This anion reacts with cationic complexes of Re, Rh, Ir, and Au, and with [{Cul(PEt3)}4] and [{Agl(PEt3)}4], to give heterometallic complexes containing a triruthenium unit. With Re, Rh, Ir, Cu, Ag, and Au, tetranuclear complexes are obtained and structures in which the heterometal atom (M′) either bridges one edge of [M′ = Cu, Ag, or Au] or caps the Ru3 triangle [M′ = Re, Rh, or Ir] are proposed. In the case of the gold complex, [Ru3{μ-Au(PMe2Ph)}(μ-H)(μ 3-PPh)(CO)9], this proposal has been confirmed by an X-ray analysis. This complex crystallises in space group P21/c with a = 8.805(3), b = 20.195(7), c = 16.683(6) Å, β = 100.62(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined by blocked-cascade least squares to R = 0.067 for 1 398 unique diffractometer data with F > 5σ(F). The reaction of the triruthenium anion with [Rh(CO)3(PR3)2] + (R = Et or Ph) gives, in addition to the tetranuclear complexes, the pentanuclear complexes [Ru3Rh2(PPh)(CO)13(PR3)]. An X-ray analysis of the complex with R = Et reveals a square-pyramidal array of metal atoms with a μ4-PPh ligand capping two of the Ru and the two Rh atoms to give an overall distorted octahedral geometry. This complex crystallises in space group C2/c with a = 20.257(5), b = 9.679(3), c = 34.726(5) Å, β = 90.24(2)°, and Z = 8. The structure was solved using the same techniques as for the Ru3Au complex and refined to R = 0.034 for 4 708 diffractometer data with F > 6σ(F).
AB - full title: Synthesis of the anion [Ru3H(μ3-PPh)(CO)9]- and its reactions with complexes of Re, Rh, Ir, Cu, Ag, and Au to give heterometallic clusters containing a triruthenium unit: Crystal structures of the complexes [Ru3Rh2(μ4-PPh)(CO)13(PEt 3)] and [Ru3{μ-Au(PMe2Ph)}(μ-H)(μ 3-PPh)(CO)9] Deprotonation of [Ru3H2(μ3-PPh)(CO)9] with base gives the anion [Ru3H(μ3-PPh)(CO)9]- which has been isolated as its [N(PPh3)2] + salt. This anion reacts with cationic complexes of Re, Rh, Ir, and Au, and with [{Cul(PEt3)}4] and [{Agl(PEt3)}4], to give heterometallic complexes containing a triruthenium unit. With Re, Rh, Ir, Cu, Ag, and Au, tetranuclear complexes are obtained and structures in which the heterometal atom (M′) either bridges one edge of [M′ = Cu, Ag, or Au] or caps the Ru3 triangle [M′ = Re, Rh, or Ir] are proposed. In the case of the gold complex, [Ru3{μ-Au(PMe2Ph)}(μ-H)(μ 3-PPh)(CO)9], this proposal has been confirmed by an X-ray analysis. This complex crystallises in space group P21/c with a = 8.805(3), b = 20.195(7), c = 16.683(6) Å, β = 100.62(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined by blocked-cascade least squares to R = 0.067 for 1 398 unique diffractometer data with F > 5σ(F). The reaction of the triruthenium anion with [Rh(CO)3(PR3)2] + (R = Et or Ph) gives, in addition to the tetranuclear complexes, the pentanuclear complexes [Ru3Rh2(PPh)(CO)13(PR3)]. An X-ray analysis of the complex with R = Et reveals a square-pyramidal array of metal atoms with a μ4-PPh ligand capping two of the Ru and the two Rh atoms to give an overall distorted octahedral geometry. This complex crystallises in space group C2/c with a = 20.257(5), b = 9.679(3), c = 34.726(5) Å, β = 90.24(2)°, and Z = 8. The structure was solved using the same techniques as for the Ru3Au complex and refined to R = 0.034 for 4 708 diffractometer data with F > 6σ(F).
UR - http://www.scopus.com/inward/record.url?scp=51149220172&partnerID=8YFLogxK
U2 - 10.1039/DT9840000959
DO - 10.1039/DT9840000959
M3 - Article
AN - SCOPUS:51149220172
SN - 1472-7773
SP - 959
EP - 967
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 5
ER -