Trinuclear osmium clusters containing bidentate Ph2PCH 2PPh2 and Me2PCH2PMe2 ligands: X-ray crystal structures of the complexes [Os3H(CO) 9(Me2PCHPMe2)] and [Os3H(OH)(CO) 8(Ph2PCH2PPh2)]

Stephen R. Hodge; Brian F. G. Johnson; Jack Lewis; Paul R. Raithby

doi:10.1039/DT9870000931

Trinuclear osmium clusters containing bidentate Ph₂PCH ₂PPh₂ and Me₂PCH₂PMe₂ ligands: X-ray crystal structures of the complexes [Os₃H(CO) ₉(Me₂PCHPMe₂)] and [Os₃H(OH)(CO) ₈(Ph₂PCH₂PPh₂)]

Stephen R. Hodge, Brian F. G. Johnson, Jack Lewis, Paul R. Raithby

University of Cambridge

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Abstract

The clusters [Os₃(CO)₁₀(dppm)] (dppm = Ph ₂PCH₂PPh₂) and [Os₃(CO) ₁₀(dmpm)] (dmpm = Me₂PCH₂PMe₂) react with trimethylamine N-oxide in acetonitrile solution to give [Os₃ CO)₉-(dppm)(MeCN)] (1) and [Os₃(CO)₉(dmpm) (MeCN)] (2) respectively. The acetonitrile ligand of (1) and (2) is readily displaced by other two-electron donor ligands to give [Os₃(CO) ₉(dppm)L] [L = PPh₃, P(OMe)₃, or Bu ^tNC] and [Os₃(CO)₉(dmpm)L] [L = P(OMe) ₃ or C₂H₄]. Thermolysis of [Os ₃(CO)₉(dmpm)(C₂H₄)] or [Os ₃(CO)₁₀(dmpm)] gives the cyclometallated product [Os ₃H (CO)₉(Me₂PCHPMe₂)]. The acetonitrile complex (1) also reacts with HX (X = Cl or SR, R = alkyl) to give clusters of general formula [Os₃H(X)(CO)₈(dppm)], whereas for X = OH or OMe the only product isolated is [Os₃H(CO) ₈{Ph₂PCH₂PPh(C₆H₄)}]. The dmpm derivative (2) reacts similarly with HCl and RSH. The cluster [Os ₃H(OH)(CO)₈(dppm)], which can be prepared from [Os ₃H-(OH)(CO)₁₀] and dppm, was found to have a different structure from [Os₃H(Cl)(CO)₈(dppm)]. All the products were characterised by i.r. and n.m.r. spectroscopy. The structures of [Os ₃H(CO)₉-(Me₂PCHPMe₂)] and [Os ₃H(OH)(CO)₈(dppm)] were confirmed by X-ray crystallography.

Original language	English
Pages (from-to)	931-937
Number of pages	7
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	4
DOIs	https://doi.org/10.1039/DT9870000931
Publication status	Published - 31 Dec 1987

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10.1039/DT9870000931

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Trinuclear osmium clusters containing bidentate Ph₂PCH ₂PPh₂ and Me₂PCH₂PMe₂ ligands: X-ray crystal structures of the complexes [Os₃H(CO) ₉(Me₂PCHPMe₂)] and [Os₃H(OH)(CO) ₈(Ph₂PCH₂PPh₂)]. / Hodge, Stephen R.; Johnson, Brian F. G.; Lewis, Jack et al.
In: Journal of the Chemical Society, Dalton Transactions, No. 4, 31.12.1987, p. 931-937.

Research output: Contribution to journal › Article › peer-review

@article{789a49a36f434eb481ecca8407dc68ad,

title = "Trinuclear osmium clusters containing bidentate Ph2PCH 2PPh2 and Me2PCH2PMe2 ligands: X-ray crystal structures of the complexes [Os3H(CO) 9(Me2PCHPMe2)] and [Os3H(OH)(CO) 8(Ph2PCH2PPh2)]",

abstract = "The clusters [Os3(CO)10(dppm)] (dppm = Ph 2PCH2PPh2) and [Os3(CO) 10(dmpm)] (dmpm = Me2PCH2PMe2) react with trimethylamine N-oxide in acetonitrile solution to give [Os3 CO)9-(dppm)(MeCN)] (1) and [Os3(CO)9(dmpm) (MeCN)] (2) respectively. The acetonitrile ligand of (1) and (2) is readily displaced by other two-electron donor ligands to give [Os3(CO) 9(dppm)L] [L = PPh3, P(OMe)3, or Bu tNC] and [Os3(CO)9(dmpm)L] [L = P(OMe) 3 or C2H4]. Thermolysis of [Os 3(CO)9(dmpm)(C2H4)] or [Os 3(CO)10(dmpm)] gives the cyclometallated product [Os 3H (CO)9(Me2PCHPMe2)]. The acetonitrile complex (1) also reacts with HX (X = Cl or SR, R = alkyl) to give clusters of general formula [Os3H(X)(CO)8(dppm)], whereas for X = OH or OMe the only product isolated is [Os3H(CO) 8{Ph2PCH2PPh(C6H4)}]. The dmpm derivative (2) reacts similarly with HCl and RSH. The cluster [Os 3H(OH)(CO)8(dppm)], which can be prepared from [Os 3H-(OH)(CO)10] and dppm, was found to have a different structure from [Os3H(Cl)(CO)8(dppm)]. All the products were characterised by i.r. and n.m.r. spectroscopy. The structures of [Os 3H(CO)9-(Me2PCHPMe2)] and [Os 3H(OH)(CO)8(dppm)] were confirmed by X-ray crystallography.",

author = "Hodge, {Stephen R.} and Johnson, {Brian F. G.} and Jack Lewis and Raithby, {Paul R.}",

year = "1987",

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doi = "10.1039/DT9870000931",

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T1 - Trinuclear osmium clusters containing bidentate Ph2PCH 2PPh2 and Me2PCH2PMe2 ligands

T2 - X-ray crystal structures of the complexes [Os3H(CO) 9(Me2PCHPMe2)] and [Os3H(OH)(CO) 8(Ph2PCH2PPh2)]

AU - Hodge, Stephen R.

AU - Johnson, Brian F. G.

AU - Lewis, Jack

AU - Raithby, Paul R.

PY - 1987/12/31

Y1 - 1987/12/31

N2 - The clusters [Os3(CO)10(dppm)] (dppm = Ph 2PCH2PPh2) and [Os3(CO) 10(dmpm)] (dmpm = Me2PCH2PMe2) react with trimethylamine N-oxide in acetonitrile solution to give [Os3 CO)9-(dppm)(MeCN)] (1) and [Os3(CO)9(dmpm) (MeCN)] (2) respectively. The acetonitrile ligand of (1) and (2) is readily displaced by other two-electron donor ligands to give [Os3(CO) 9(dppm)L] [L = PPh3, P(OMe)3, or Bu tNC] and [Os3(CO)9(dmpm)L] [L = P(OMe) 3 or C2H4]. Thermolysis of [Os 3(CO)9(dmpm)(C2H4)] or [Os 3(CO)10(dmpm)] gives the cyclometallated product [Os 3H (CO)9(Me2PCHPMe2)]. The acetonitrile complex (1) also reacts with HX (X = Cl or SR, R = alkyl) to give clusters of general formula [Os3H(X)(CO)8(dppm)], whereas for X = OH or OMe the only product isolated is [Os3H(CO) 8{Ph2PCH2PPh(C6H4)}]. The dmpm derivative (2) reacts similarly with HCl and RSH. The cluster [Os 3H(OH)(CO)8(dppm)], which can be prepared from [Os 3H-(OH)(CO)10] and dppm, was found to have a different structure from [Os3H(Cl)(CO)8(dppm)]. All the products were characterised by i.r. and n.m.r. spectroscopy. The structures of [Os 3H(CO)9-(Me2PCHPMe2)] and [Os 3H(OH)(CO)8(dppm)] were confirmed by X-ray crystallography.

AB - The clusters [Os3(CO)10(dppm)] (dppm = Ph 2PCH2PPh2) and [Os3(CO) 10(dmpm)] (dmpm = Me2PCH2PMe2) react with trimethylamine N-oxide in acetonitrile solution to give [Os3 CO)9-(dppm)(MeCN)] (1) and [Os3(CO)9(dmpm) (MeCN)] (2) respectively. The acetonitrile ligand of (1) and (2) is readily displaced by other two-electron donor ligands to give [Os3(CO) 9(dppm)L] [L = PPh3, P(OMe)3, or Bu tNC] and [Os3(CO)9(dmpm)L] [L = P(OMe) 3 or C2H4]. Thermolysis of [Os 3(CO)9(dmpm)(C2H4)] or [Os 3(CO)10(dmpm)] gives the cyclometallated product [Os 3H (CO)9(Me2PCHPMe2)]. The acetonitrile complex (1) also reacts with HX (X = Cl or SR, R = alkyl) to give clusters of general formula [Os3H(X)(CO)8(dppm)], whereas for X = OH or OMe the only product isolated is [Os3H(CO) 8{Ph2PCH2PPh(C6H4)}]. The dmpm derivative (2) reacts similarly with HCl and RSH. The cluster [Os 3H(OH)(CO)8(dppm)], which can be prepared from [Os 3H-(OH)(CO)10] and dppm, was found to have a different structure from [Os3H(Cl)(CO)8(dppm)]. All the products were characterised by i.r. and n.m.r. spectroscopy. The structures of [Os 3H(CO)9-(Me2PCHPMe2)] and [Os 3H(OH)(CO)8(dppm)] were confirmed by X-ray crystallography.

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DO - 10.1039/DT9870000931

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Trinuclear osmium clusters containing bidentate Ph₂PCH ₂PPh₂ and Me₂PCH₂PMe₂ ligands: X-ray crystal structures of the complexes [Os₃H(CO) ₉(Me₂PCHPMe₂)] and [Os₃H(OH)(CO) ₈(Ph₂PCH₂PPh₂)]

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