TY - JOUR
T1 - Ruthenium Cluster Chemistry with Ph2PC6H4-4-C = CH
AU - Lucas, Nigel T.
AU - Cifuentes, Marie P.
AU - Nguyen, Lam T.
AU - Humphrey, Mark G.
N1 - © 2001 The Author(s)
PY - 2001
Y1 - 2001
N2 - The new phosphines Ph2PC6H4-4-C = CR [R = SiMe3 (1), H (2)] have been used to prepare Ru3(CO)9(Ph2PC6H4-4-C = CSiMe3)3 (4) and Ru(C = CC6H4-4-PPh2)(PPh3) 2(η-C5H5) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru3(CO)9(Ph2PC6H4-4-C = CH)3 (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh3)2(η-C5H5)]PF 6 or reaction of Ru3(CO)12 with 3 gives Ru3(CO)9{(Ph2PC6H4-4-C = C)Ru(PPh3)2(η-C5H5)}3 (6). Complexes 3-6 have been studied by cyclic voltammetry. Proceeding from Ru3(CO)12 to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C6H14: space group P1, a = 12.760(1) Å, b = 17.077(1) Å, c = 17.924(2) Å, α = 108.656(5)°, β = 96.344(5)°, γ = 93.523(5)°, V = 3658.4(6) Å3, Z = 2, R = 0.078, Rw = 0.105 for 5008 reflections [I > 2.00σ(I)].
AB - The new phosphines Ph2PC6H4-4-C = CR [R = SiMe3 (1), H (2)] have been used to prepare Ru3(CO)9(Ph2PC6H4-4-C = CSiMe3)3 (4) and Ru(C = CC6H4-4-PPh2)(PPh3) 2(η-C5H5) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru3(CO)9(Ph2PC6H4-4-C = CH)3 (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh3)2(η-C5H5)]PF 6 or reaction of Ru3(CO)12 with 3 gives Ru3(CO)9{(Ph2PC6H4-4-C = C)Ru(PPh3)2(η-C5H5)}3 (6). Complexes 3-6 have been studied by cyclic voltammetry. Proceeding from Ru3(CO)12 to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C6H14: space group P1, a = 12.760(1) Å, b = 17.077(1) Å, c = 17.924(2) Å, α = 108.656(5)°, β = 96.344(5)°, γ = 93.523(5)°, V = 3658.4(6) Å3, Z = 2, R = 0.078, Rw = 0.105 for 5008 reflections [I > 2.00σ(I)].
KW - Alkynyl
KW - Carbonyl
KW - Electrochemistry
KW - Phosphine
KW - Ruthenium
KW - X-ray structure
UR - http://www.scopus.com/inward/record.url?scp=0035595715&partnerID=8YFLogxK
U2 - 10.1023/A:1016683331367
DO - 10.1023/A:1016683331367
M3 - Article
SN - 1040-7278
VL - 12
SP - 201
EP - 221
JO - Journal of Cluster Science
JF - Journal of Cluster Science
IS - 1
ER -