Reactions of the co-ordinatively unsaturated cluster [os3(μ-H)(CO)8{Ph2PCH2P(Ph)C 6H4}] with alkynes RC≡CR (R = Ph, C6H4Me, Me or CF3); Crystal structures of [os3(CO)8{μ3-η 2(∥)-RC2R}(Ph2PCH2PPh...

Michael P. Brown; P. Ann Dolby; Marjorie M. Harding; A. Jane Mathews; Anthony K. Smith; Domenico Osella; Mauro Arbrun; Roberto Gobetto; Paul R. Raithby; Piero Zanello

doi:10.1039/DT9930000827

Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh...

Michael P. Brown
, P. Ann Dolby
, Marjorie M. Harding
, A. Jane Mathews
, Anthony K. Smith
, Domenico Osella
, Mauro Arbrun
, Roberto Gobetto
, Paul R. Raithby
, Piero Zanello

University of Liverpool
University of Turin
University of Cambridge
Università degli Studi di Siena

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

Abstract

Full title: Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh ₂)] (R = Me or CF₃) and electrochemical behaviour of triosmium-alkyne clusters. Treatment of the unsaturated triosmium cluster [Os₃(μ-H)(CO)₈{μ-Ph₂PCH ₂P(Ph)C₆H₄}] 1 with diphenylacetylene leads to the formation of [Os₃(CO)₇(PhC₂Ph)(Ph₂PCH ₂PPh₂)] 2a in which the alkyne is bonded in a μ₃-η² (⊥) mode. Addition of CO to 2a gives [Os₃(CO)₇(μ-CO)(RC₂R)(Ph₂PCH ₂PPh₂)] 3a (R = Ph) in which the alkyne is bonded in a μ₃-η²(∥) mode. Two-electron electrochemical reduction of 2a also causes this change in co-ordination mode of the alkyne ligand. Protonation of the electrochemically produced dianion [Os₃(CO)₇{μ₃-η ²(∥)PhC₂Ph}(Ph₂PCH₂PPh ₂)]^2- gives [Os₃(μ-H)₂(CO)₇{μ₃-η ²(∥)-PhC₂Ph}(Ph₂PCH₂PPh ₂)] 4. The same product 4 has also been obtained by direct hydrogenation of 2a. A similar chemical and electrochemical behaviour is observed for the ditolylacetylene derivative [Os₃(CO)₇(p-MeC₆H₄C ₂C₆H₄Me-p)(Ph₂PCH ₂PPh₂)] 2b, where the two p-methyl substituents are diagnostic in ¹H NMR spectroscopy. With the alkynes RC≡CR (R = Me or CF₃), analogous complexes to 2 are not observed, instead complexes [Os₃(CO)₈{μ₃-η ²(∥)-RR}(Ph₂PCH₂PPh₂)] 3c (R = Me) and 3d (R = CF₃) are obtained. Single-crystal X-ray structure determinations of 3c and 3d have been performed.

Original language	English
Pages (from-to)	827-834
Number of pages	8
Journal	Journal of the Chemical Society, Dalton Transactions
Issue number	6
DOIs	https://doi.org/10.1039/DT9930000827
Publication status	Published - 1993

ASJC Scopus subject areas

General Chemistry

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Dive into the research topics of 'Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh...'. Together they form a unique fingerprint.

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Brown, M. P., Dolby, P. A., Harding, M. M., Mathews, A. J., Smith, A. K., Osella, D., Arbrun, M., Gobetto, R., Raithby, P. R., & Zanello, P. (1993). Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh... Journal of the Chemical Society, Dalton Transactions, (6), 827-834. https://doi.org/10.1039/DT9930000827

Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh... / Brown, Michael P.; Dolby, P. Ann; Harding, Marjorie M. et al.
In: Journal of the Chemical Society, Dalton Transactions, No. 6, 1993, p. 827-834.

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

Brown, MP, Dolby, PA, Harding, MM, Mathews, AJ, Smith, AK, Osella, D, Arbrun, M, Gobetto, R, Raithby, PR & Zanello, P 1993, 'Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh...', Journal of the Chemical Society, Dalton Transactions, no. 6, pp. 827-834. https://doi.org/10.1039/DT9930000827

Brown MP, Dolby PA, Harding MM, Mathews AJ, Smith AK, Osella D et al. Reactions of the co-ordinatively unsaturated cluster [os₃(μ-H)(CO)₈{Ph₂PCH₂P(Ph)C ₆H₄}] with alkynes RC≡CR (R = Ph, C₆H₄Me, Me or CF₃); Crystal structures of [os₃(CO)₈{μ₃-η ²(∥)-RC₂R}(Ph₂PCH₂PPh... Journal of the Chemical Society, Dalton Transactions. 1993;(6):827-834. doi: 10.1039/DT9930000827

@article{3581b81b22a745c5a27718d184ec66d7,

title = "Reactions of the co-ordinatively unsaturated cluster [os3(μ-H)(CO)8\{Ph2PCH2P(Ph)C 6H4\}] with alkynes RC≡CR (R = Ph, C6H4Me, Me or CF3); Crystal structures of [os3(CO)8\{μ3-η 2(∥)-RC2R\}(Ph2PCH2PPh...",

abstract = "Full title: Reactions of the co-ordinatively unsaturated cluster [os3(μ-H)(CO)8\{Ph2PCH2P(Ph)C 6H4\}] with alkynes RC≡CR (R = Ph, C6H4Me, Me or CF3); Crystal structures of [os3(CO)8\{μ3-η 2(∥)-RC2R\}(Ph2PCH2PPh 2)] (R = Me or CF3) and electrochemical behaviour of triosmium-alkyne clusters. Treatment of the unsaturated triosmium cluster [Os3(μ-H)(CO)8\{μ-Ph2PCH 2P(Ph)C6H4\}] 1 with diphenylacetylene leads to the formation of [Os3(CO)7(PhC2Ph)(Ph2PCH 2PPh2)] 2a in which the alkyne is bonded in a μ3-η2 (⊥) mode. Addition of CO to 2a gives [Os3(CO)7(μ-CO)(RC2R)(Ph2PCH 2PPh2)] 3a (R = Ph) in which the alkyne is bonded in a μ3-η2(∥) mode. Two-electron electrochemical reduction of 2a also causes this change in co-ordination mode of the alkyne ligand. Protonation of the electrochemically produced dianion [Os3(CO)7\{μ3-η 2(∥)PhC2Ph\}(Ph2PCH2PPh 2)]2- gives [Os3(μ-H)2(CO)7\{μ3-η 2(∥)-PhC2Ph\}(Ph2PCH2PPh 2)] 4. The same product 4 has also been obtained by direct hydrogenation of 2a. A similar chemical and electrochemical behaviour is observed for the ditolylacetylene derivative [Os3(CO)7(p-MeC6H4C 2C6H4Me-p)(Ph2PCH 2PPh2)] 2b, where the two p-methyl substituents are diagnostic in 1H NMR spectroscopy. With the alkynes RC≡CR (R = Me or CF3), analogous complexes to 2 are not observed, instead complexes [Os3(CO)8\{μ3-η 2(∥)-RR\}(Ph2PCH2PPh2)] 3c (R = Me) and 3d (R = CF3) are obtained. Single-crystal X-ray structure determinations of 3c and 3d have been performed.",

author = "Brown, \{Michael P.\} and Dolby, \{P. Ann\} and Harding, \{Marjorie M.\} and Mathews, \{A. Jane\} and Smith, \{Anthony K.\} and Domenico Osella and Mauro Arbrun and Roberto Gobetto and Raithby, \{Paul R.\} and Piero Zanello",

year = "1993",

doi = "10.1039/DT9930000827",

language = "English",

pages = "827--834",

journal = "Journal of the Chemical Society, Dalton Transactions",

issn = "1472-7773",

publisher = "Royal Society of Chemistry",

number = "6",

}

TY - JOUR

T1 - Reactions of the co-ordinatively unsaturated cluster [os3(μ-H)(CO)8{Ph2PCH2P(Ph)C 6H4}] with alkynes RC≡CR (R = Ph, C6H4Me, Me or CF3); Crystal structures of [os3(CO)8{μ3-η 2(∥)-RC2R}(Ph2PCH2PPh...

AU - Brown, Michael P.

AU - Dolby, P. Ann

AU - Harding, Marjorie M.

AU - Mathews, A. Jane

AU - Smith, Anthony K.

AU - Osella, Domenico

AU - Arbrun, Mauro

AU - Gobetto, Roberto

AU - Raithby, Paul R.

AU - Zanello, Piero

PY - 1993

Y1 - 1993

N2 - Full title: Reactions of the co-ordinatively unsaturated cluster [os3(μ-H)(CO)8{Ph2PCH2P(Ph)C 6H4}] with alkynes RC≡CR (R = Ph, C6H4Me, Me or CF3); Crystal structures of [os3(CO)8{μ3-η 2(∥)-RC2R}(Ph2PCH2PPh 2)] (R = Me or CF3) and electrochemical behaviour of triosmium-alkyne clusters. Treatment of the unsaturated triosmium cluster [Os3(μ-H)(CO)8{μ-Ph2PCH 2P(Ph)C6H4}] 1 with diphenylacetylene leads to the formation of [Os3(CO)7(PhC2Ph)(Ph2PCH 2PPh2)] 2a in which the alkyne is bonded in a μ3-η2 (⊥) mode. Addition of CO to 2a gives [Os3(CO)7(μ-CO)(RC2R)(Ph2PCH 2PPh2)] 3a (R = Ph) in which the alkyne is bonded in a μ3-η2(∥) mode. Two-electron electrochemical reduction of 2a also causes this change in co-ordination mode of the alkyne ligand. Protonation of the electrochemically produced dianion [Os3(CO)7{μ3-η 2(∥)PhC2Ph}(Ph2PCH2PPh 2)]2- gives [Os3(μ-H)2(CO)7{μ3-η 2(∥)-PhC2Ph}(Ph2PCH2PPh 2)] 4. The same product 4 has also been obtained by direct hydrogenation of 2a. A similar chemical and electrochemical behaviour is observed for the ditolylacetylene derivative [Os3(CO)7(p-MeC6H4C 2C6H4Me-p)(Ph2PCH 2PPh2)] 2b, where the two p-methyl substituents are diagnostic in 1H NMR spectroscopy. With the alkynes RC≡CR (R = Me or CF3), analogous complexes to 2 are not observed, instead complexes [Os3(CO)8{μ3-η 2(∥)-RR}(Ph2PCH2PPh2)] 3c (R = Me) and 3d (R = CF3) are obtained. Single-crystal X-ray structure determinations of 3c and 3d have been performed.

AB - Full title: Reactions of the co-ordinatively unsaturated cluster [os3(μ-H)(CO)8{Ph2PCH2P(Ph)C 6H4}] with alkynes RC≡CR (R = Ph, C6H4Me, Me or CF3); Crystal structures of [os3(CO)8{μ3-η 2(∥)-RC2R}(Ph2PCH2PPh 2)] (R = Me or CF3) and electrochemical behaviour of triosmium-alkyne clusters. Treatment of the unsaturated triosmium cluster [Os3(μ-H)(CO)8{μ-Ph2PCH 2P(Ph)C6H4}] 1 with diphenylacetylene leads to the formation of [Os3(CO)7(PhC2Ph)(Ph2PCH 2PPh2)] 2a in which the alkyne is bonded in a μ3-η2 (⊥) mode. Addition of CO to 2a gives [Os3(CO)7(μ-CO)(RC2R)(Ph2PCH 2PPh2)] 3a (R = Ph) in which the alkyne is bonded in a μ3-η2(∥) mode. Two-electron electrochemical reduction of 2a also causes this change in co-ordination mode of the alkyne ligand. Protonation of the electrochemically produced dianion [Os3(CO)7{μ3-η 2(∥)PhC2Ph}(Ph2PCH2PPh 2)]2- gives [Os3(μ-H)2(CO)7{μ3-η 2(∥)-PhC2Ph}(Ph2PCH2PPh 2)] 4. The same product 4 has also been obtained by direct hydrogenation of 2a. A similar chemical and electrochemical behaviour is observed for the ditolylacetylene derivative [Os3(CO)7(p-MeC6H4C 2C6H4Me-p)(Ph2PCH 2PPh2)] 2b, where the two p-methyl substituents are diagnostic in 1H NMR spectroscopy. With the alkynes RC≡CR (R = Me or CF3), analogous complexes to 2 are not observed, instead complexes [Os3(CO)8{μ3-η 2(∥)-RR}(Ph2PCH2PPh2)] 3c (R = Me) and 3d (R = CF3) are obtained. Single-crystal X-ray structure determinations of 3c and 3d have been performed.

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U2 - 10.1039/DT9930000827

DO - 10.1039/DT9930000827

M3 - Article

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SN - 1472-7773

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JO - Journal of the Chemical Society, Dalton Transactions

JF - Journal of the Chemical Society, Dalton Transactions

IS - 6

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