Backbone modified small bite-angle diphosphines: Synthesis, structure, and DFT evaluation of the thermal activation products based on Os3(CO)10{μ-Ph2PC(Me)2PPh2}

Jagodish C. Sarker; Arun K. Raha; Shishir Ghosh; Graeme Hogarth; Shariff E. Kabir; Michael G. Richmond

doi:10.1016/j.jorganchem.2013.10.042

Backbone modified small bite-angle diphosphines: Synthesis, structure, and DFT evaluation of the thermal activation products based on Os3(CO)10{μ-Ph2PC(Me)2PPh2}

Jagodish C. Sarker, Arun K. Raha, Shishir Ghosh, Graeme Hogarth, Shariff E. Kabir, Michael G. Richmond

Chemistry

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

8 Citations (Scopus)

Abstract

Addition of 2,2'-bis(diphenylphosphino)propane, Ph2PC(Me)2PPh2 (dppmMe2), to Os3(CO)10(MeCN)2 at room temperature affords Os3(CO)10{μ-Ph2PC(Me)2PPh2} (1-Me2), whose X-ray diffraction has been established and found to contain a bridging diphosphine ligand. Heating 1-Me2 in toluene results in the formation of the expected orthometalated addition product Os3(CO)8{μ3-Ph2PC(Me)2P(Ph)C6H4}(μ-H) (2-Me2) in only trace amounts, with the face-capped cluster Os3(CO)9{μ3-PhPC(Me)2P(Ph)C6H4} (3-Me2) formed as the major product as a result of elimination of benzene. The conversion of 1-Me2 to 2-Me2 has been investigated by density functional theory (DFT) calculations and the potential energy surface has been mapped out. The observed reactivity in the dppmMe2-substituted cluster 1-Me2 is compared with the related dppmH2- and dppmHMe-substituted triosmium complexes.

Original language	English
Pages (from-to)	49-58
Number of pages	10
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	750
DOIs	https://doi.org/10.1016/j.jorganchem.2013.10.042
Publication status	Published - 15 Jan 2014

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10.1016/j.jorganchem.2013.10.042

http://linkinghub.elsevier.com/retrieve/pii/S0022328X13007821

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@article{eb755b54d5b445abaa8382239d5460ed,

title = "Backbone modified small bite-angle diphosphines: Synthesis, structure, and DFT evaluation of the thermal activation products based on Os3(CO)10{μ-Ph2PC(Me)2PPh2}",

abstract = "Addition of 2,2'-bis(diphenylphosphino)propane, Ph2PC(Me)2PPh2 (dppmMe2), to Os3(CO)10(MeCN)2 at room temperature affords Os3(CO)10{μ-Ph2PC(Me)2PPh2} (1-Me2), whose X-ray diffraction has been established and found to contain a bridging diphosphine ligand. Heating 1-Me2 in toluene results in the formation of the expected orthometalated addition product Os3(CO)8{μ3-Ph2PC(Me)2P(Ph)C6H4}(μ-H) (2-Me2) in only trace amounts, with the face-capped cluster Os3(CO)9{μ3-PhPC(Me)2P(Ph)C6H4} (3-Me2) formed as the major product as a result of elimination of benzene. The conversion of 1-Me2 to 2-Me2 has been investigated by density functional theory (DFT) calculations and the potential energy surface has been mapped out. The observed reactivity in the dppmMe2-substituted cluster 1-Me2 is compared with the related dppmH2- and dppmHMe-substituted triosmium complexes.",

author = "Sarker, {Jagodish C.} and Raha, {Arun K.} and Shishir Ghosh and Graeme Hogarth and Kabir, {Shariff E.} and Richmond, {Michael G.}",

year = "2014",

month = jan,

day = "15",

doi = "10.1016/j.jorganchem.2013.10.042",

language = "English",

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T1 - Backbone modified small bite-angle diphosphines

T2 - Synthesis, structure, and DFT evaluation of the thermal activation products based on Os3(CO)10{μ-Ph2PC(Me)2PPh2}

AU - Sarker, Jagodish C.

AU - Raha, Arun K.

AU - Ghosh, Shishir

AU - Hogarth, Graeme

AU - Kabir, Shariff E.

AU - Richmond, Michael G.

PY - 2014/1/15

Y1 - 2014/1/15

N2 - Addition of 2,2'-bis(diphenylphosphino)propane, Ph2PC(Me)2PPh2 (dppmMe2), to Os3(CO)10(MeCN)2 at room temperature affords Os3(CO)10{μ-Ph2PC(Me)2PPh2} (1-Me2), whose X-ray diffraction has been established and found to contain a bridging diphosphine ligand. Heating 1-Me2 in toluene results in the formation of the expected orthometalated addition product Os3(CO)8{μ3-Ph2PC(Me)2P(Ph)C6H4}(μ-H) (2-Me2) in only trace amounts, with the face-capped cluster Os3(CO)9{μ3-PhPC(Me)2P(Ph)C6H4} (3-Me2) formed as the major product as a result of elimination of benzene. The conversion of 1-Me2 to 2-Me2 has been investigated by density functional theory (DFT) calculations and the potential energy surface has been mapped out. The observed reactivity in the dppmMe2-substituted cluster 1-Me2 is compared with the related dppmH2- and dppmHMe-substituted triosmium complexes.

AB - Addition of 2,2'-bis(diphenylphosphino)propane, Ph2PC(Me)2PPh2 (dppmMe2), to Os3(CO)10(MeCN)2 at room temperature affords Os3(CO)10{μ-Ph2PC(Me)2PPh2} (1-Me2), whose X-ray diffraction has been established and found to contain a bridging diphosphine ligand. Heating 1-Me2 in toluene results in the formation of the expected orthometalated addition product Os3(CO)8{μ3-Ph2PC(Me)2P(Ph)C6H4}(μ-H) (2-Me2) in only trace amounts, with the face-capped cluster Os3(CO)9{μ3-PhPC(Me)2P(Ph)C6H4} (3-Me2) formed as the major product as a result of elimination of benzene. The conversion of 1-Me2 to 2-Me2 has been investigated by density functional theory (DFT) calculations and the potential energy surface has been mapped out. The observed reactivity in the dppmMe2-substituted cluster 1-Me2 is compared with the related dppmH2- and dppmHMe-substituted triosmium complexes.

U2 - 10.1016/j.jorganchem.2013.10.042

DO - 10.1016/j.jorganchem.2013.10.042

M3 - Article

SN - 0022-328X

VL - 750

SP - 49

EP - 58

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

ER -

Backbone modified small bite-angle diphosphines: Synthesis, structure, and DFT evaluation of the thermal activation products based on Os3(CO)10{μ-Ph2PC(Me)2PPh2}

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