Oxidative-addition of germanium-hydrogen bonds to triosmium centers: Reactions of Os3(CO)10(μ-dppm) and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH

Mohd Rezaul Haque; Md Jakir Hossain; Ahibur Rahaman; Shishir Ghosh; Shariff E. Kabir; Graeme Hogarth; Derek A. Tocher

doi:10.1016/j.jorganchem.2015.05.060

Oxidative-addition of germanium-hydrogen bonds to triosmium centers: Reactions of Os₃(CO)₁₀(μ-dppm) and Os₃(CO)₈(μ₃-Ph₂PCH₂P(Ph)C₆H₄)(μ-H) with Ph₃GeH

Mohd Rezaul Haque, Md Jakir Hossain, Ahibur Rahaman, Shishir Ghosh, Shariff E. Kabir^*, Graeme Hogarth, Derek A. Tocher

^*Corresponding author for this work

Chemistry

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Abstract

Reactions of the triosmium clusters Os₃(CO)₁₀(μ-dppm) [dppm = bis(diphenylphosphino)methane] and Os₃(CO)₈(μ₃-Ph₂PCH₂P(Ph)C₆H₄)(μ-H) with Ph₃GeH are described. With Os₃(CO)₁₀(μ-dppm) at 110 °C the oxidative-addition product Os₃(CO)₉(GePh₃)(μ-dppm)(μ-H) (1) initially results, but further decarbonylates upon prolonged heating to give 46-electron Os₃(CO)₇(GePh₃)(μ₃-Ph₂PCH₂P(Ph)C₆H₄)(μ-H)₂ (2) resulting from C-H bond activation of the diphosphine. The pre-activated Os₃(CO)₈(μ₃-Ph₂PCH₂P(Ph)C₆H₄)(μ-H) reacts with Ph₃GeH under milder conditions (40 °C) to afford Os₃(CO)₈(GePh₃)₂(μ-dppm)(μ-H)₂ (3) together with 1. Cluster 3 converts into 2 upon heating and the direct reaction between Os₃(CO)₈(μ₃-Ph₂PCH₂P(Ph)C₆H₄)(μ-H) and Ph₃GeH at 110 °C also produces 2. All these clusters have been structurally characterized by single crystal X-ray diffraction analysis.

Original language	English
Pages (from-to)	240-246
Number of pages	7
Journal	JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume	812
Early online date	1 Jun 2015
DOIs	https://doi.org/10.1016/j.jorganchem.2015.05.060
Publication status	Published - 15 Jun 2016

Keywords

Bis(diphenylphosphino)methane (dppm)
Carbonyls
Oxidative-addition of Ge-H bond
Triosmium clusters
Triphenylgermanium hydride (PhGeH)
X-ray structures

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10.1016/j.jorganchem.2015.05.060

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@article{cebd98c1a0434431870c52dbd7e28c13,

title = "Oxidative-addition of germanium-hydrogen bonds to triosmium centers: Reactions of Os3(CO)10(μ-dppm) and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH",

abstract = "Reactions of the triosmium clusters Os3(CO)10(μ-dppm) [dppm = bis(diphenylphosphino)methane] and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH are described. With Os3(CO)10(μ-dppm) at 110 °C the oxidative-addition product Os3(CO)9(GePh3)(μ-dppm)(μ-H) (1) initially results, but further decarbonylates upon prolonged heating to give 46-electron Os3(CO)7(GePh3)(μ3-Ph2PCH2P(Ph)C6H4)(μ-H)2 (2) resulting from C-H bond activation of the diphosphine. The pre-activated Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) reacts with Ph3GeH under milder conditions (40 °C) to afford Os3(CO)8(GePh3)2(μ-dppm)(μ-H)2 (3) together with 1. Cluster 3 converts into 2 upon heating and the direct reaction between Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) and Ph3GeH at 110 °C also produces 2. All these clusters have been structurally characterized by single crystal X-ray diffraction analysis.",

keywords = "Bis(diphenylphosphino)methane (dppm), Carbonyls, Oxidative-addition of Ge-H bond, Triosmium clusters, Triphenylgermanium hydride (PhGeH), X-ray structures",

author = "Haque, {Mohd Rezaul} and Hossain, {Md Jakir} and Ahibur Rahaman and Shishir Ghosh and Kabir, {Shariff E.} and Graeme Hogarth and Tocher, {Derek A.}",

year = "2016",

month = jun,

day = "15",

doi = "10.1016/j.jorganchem.2015.05.060",

language = "English",

volume = "812",

pages = "240--246",

journal = "JOURNAL OF ORGANOMETALLIC CHEMISTRY",

issn = "0022-328X",

publisher = "Elsevier",

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TY - JOUR

T1 - Oxidative-addition of germanium-hydrogen bonds to triosmium centers

T2 - Reactions of Os3(CO)10(μ-dppm) and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH

AU - Haque, Mohd Rezaul

AU - Hossain, Md Jakir

AU - Rahaman, Ahibur

AU - Ghosh, Shishir

AU - Kabir, Shariff E.

AU - Hogarth, Graeme

AU - Tocher, Derek A.

PY - 2016/6/15

Y1 - 2016/6/15

N2 - Reactions of the triosmium clusters Os3(CO)10(μ-dppm) [dppm = bis(diphenylphosphino)methane] and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH are described. With Os3(CO)10(μ-dppm) at 110 °C the oxidative-addition product Os3(CO)9(GePh3)(μ-dppm)(μ-H) (1) initially results, but further decarbonylates upon prolonged heating to give 46-electron Os3(CO)7(GePh3)(μ3-Ph2PCH2P(Ph)C6H4)(μ-H)2 (2) resulting from C-H bond activation of the diphosphine. The pre-activated Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) reacts with Ph3GeH under milder conditions (40 °C) to afford Os3(CO)8(GePh3)2(μ-dppm)(μ-H)2 (3) together with 1. Cluster 3 converts into 2 upon heating and the direct reaction between Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) and Ph3GeH at 110 °C also produces 2. All these clusters have been structurally characterized by single crystal X-ray diffraction analysis.

AB - Reactions of the triosmium clusters Os3(CO)10(μ-dppm) [dppm = bis(diphenylphosphino)methane] and Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) with Ph3GeH are described. With Os3(CO)10(μ-dppm) at 110 °C the oxidative-addition product Os3(CO)9(GePh3)(μ-dppm)(μ-H) (1) initially results, but further decarbonylates upon prolonged heating to give 46-electron Os3(CO)7(GePh3)(μ3-Ph2PCH2P(Ph)C6H4)(μ-H)2 (2) resulting from C-H bond activation of the diphosphine. The pre-activated Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) reacts with Ph3GeH under milder conditions (40 °C) to afford Os3(CO)8(GePh3)2(μ-dppm)(μ-H)2 (3) together with 1. Cluster 3 converts into 2 upon heating and the direct reaction between Os3(CO)8(μ3-Ph2PCH2P(Ph)C6H4)(μ-H) and Ph3GeH at 110 °C also produces 2. All these clusters have been structurally characterized by single crystal X-ray diffraction analysis.

KW - Bis(diphenylphosphino)methane (dppm)

KW - Carbonyls

KW - Oxidative-addition of Ge-H bond

KW - Triosmium clusters

KW - Triphenylgermanium hydride (PhGeH)

KW - X-ray structures

UR - http://www.scopus.com/inward/record.url?scp=84933566846&partnerID=8YFLogxK

U2 - 10.1016/j.jorganchem.2015.05.060

DO - 10.1016/j.jorganchem.2015.05.060

M3 - Article

AN - SCOPUS:84933566846

SN - 0022-328X

VL - 812

SP - 240

EP - 246

JO - JOURNAL OF ORGANOMETALLIC CHEMISTRY

JF - JOURNAL OF ORGANOMETALLIC CHEMISTRY

ER -

Oxidative-addition of germanium-hydrogen bonds to triosmium centers: Reactions of Os₃(CO)₁₀(μ-dppm) and Os₃(CO)₈(μ₃-Ph₂PCH₂P(Ph)C₆H₄)(μ-H) with Ph₃GeH

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