TY - JOUR
T1 - Synthesis, reactivity, and X-ray crystal structure of the cationic cluster complex [Os4H3(CO)12(NCMe)2][BF4]
AU - Johnson, Brian F.G.
AU - Lewis, Jack
AU - Nelson, William J.H.
AU - Puga, José
AU - Raithby, Paul R.
AU - Whitmire, Kenton H.
PY - 1983/12/31
Y1 - 1983/12/31
N2 - The anion [Os4H3(CO)12]- reacts with NOX (X = BF4 or PF6) in MeCN to give the salt [Os4H3(CO)12(NCMe)2]X in moderate yield. The fluoroborate salt crystallises in space group P21/c with a = 17.555(7), b = 9.252(4), c = 17.767(8) Å, β = 108.93(3)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined to a converged R = 0.049 for 3 454 diffractometer data. The four Os atoms in the cation adopt a 'butterfly' arrangement with 4.338(2) Å between the two 'wingtip' Os atoms. Each of these two metal atoms is co-ordinated to three carbonyl ligands and an axial acetonitrile ligand oriented away from the centre of the cluster. Each of the two 'hinge' Os atoms has three terminal carbonyl groups associated with it. The [Os4H3(CO)12(NCMe)2]+ cation reacts with X- (X = Cl or I) to give the neutral complex [Os4H3(CO)12X], and with NO2- to give the cluster anion [Os4H(CO)12(NCMe)2]-. Protonation of this anion regenerates the title cation. The anion reacts with Au(PPh3)Cl to produce the neutral mixed-metal cluster [Os4H(CO)12(NCMe)2{Au(PPh3)}], a derivative of the unobserved neutral molecule [Os4H2(CO)12(NCMe)2].
AB - The anion [Os4H3(CO)12]- reacts with NOX (X = BF4 or PF6) in MeCN to give the salt [Os4H3(CO)12(NCMe)2]X in moderate yield. The fluoroborate salt crystallises in space group P21/c with a = 17.555(7), b = 9.252(4), c = 17.767(8) Å, β = 108.93(3)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier-difference techniques, and refined to a converged R = 0.049 for 3 454 diffractometer data. The four Os atoms in the cation adopt a 'butterfly' arrangement with 4.338(2) Å between the two 'wingtip' Os atoms. Each of these two metal atoms is co-ordinated to three carbonyl ligands and an axial acetonitrile ligand oriented away from the centre of the cluster. Each of the two 'hinge' Os atoms has three terminal carbonyl groups associated with it. The [Os4H3(CO)12(NCMe)2]+ cation reacts with X- (X = Cl or I) to give the neutral complex [Os4H3(CO)12X], and with NO2- to give the cluster anion [Os4H(CO)12(NCMe)2]-. Protonation of this anion regenerates the title cation. The anion reacts with Au(PPh3)Cl to produce the neutral mixed-metal cluster [Os4H(CO)12(NCMe)2{Au(PPh3)}], a derivative of the unobserved neutral molecule [Os4H2(CO)12(NCMe)2].
UR - https://www.scopus.com/pages/publications/37049110413
U2 - 10.1039/DT9830001339
DO - 10.1039/DT9830001339
M3 - Article
AN - SCOPUS:37049110413
SN - 1472-7773
SP - 1339
EP - 1344
JO - Journal of the Chemical Society, Dalton Transactions
JF - Journal of the Chemical Society, Dalton Transactions
IS - 7
ER -