Reactions of the lightly-stabilized triosmium cluster Os3(CO)8{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) with two-electron donor ligands

Jagodish C. Sarker; Saifur Rahman; Shishir Ghosh; Graeme Hogarth; Shariff E. Kabir

doi:10.1016/j.poly.2020.114608

Reactions of the lightly-stabilized triosmium cluster Os₃(CO)₈{μ₃-Ph₂PCH(Me)P(Ph)C₆H₄}(μ-H) with two-electron donor ligands

Jagodish C. Sarker, Saifur Rahman, Shishir Ghosh, Graeme Hogarth^*, Shariff E. Kabir

^*Corresponding author for this work

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Abstract

Reactions of the lightly-stabilized Os₃(CO)₈{μ₃-Ph₂PCH(Me)P(Ph)C₆H₄}(μ-H) (1) with dihydrogen and representative 2-electron donor ligands, PPh₃ and P(OMe)₃, are described. With PPh₃, the phosphine-adduct Os₃(CO)₈(PPh₃){μ₃-Ph₂PCH(Me)P(Ph)C₆H₄}(μ-H) (2) is initially formed but this reacts further via three separate pathways: adding a second equivalent of PPh₃ to yield Os₃(CO)₈(PPh₃)₂{μ-Ph₂PCH(Me)PPh₂} (5), losing a CO ligand with concomitant phosphine migration to afford Os₃(CO)₇(PPh₃){μ₃-Ph₂PCH(Me)P(Ph)C₆H₄}(μ-H) (3) or adding a CO ligand to yield Os₃(CO)₉(PPh₃){μ-Ph₂PCH(Me)PPh₂} (4). In contrast, reaction with P(OMe)₃ leads to the simple stepwise formation of the mono- and bis-phosphite adducts, Os₃(CO)₈{P(OMe)₃}{μ₃-Ph₂PCH(Me)P(Ph)C₆H₄}(μ-H) (6) and Os₃(CO)₈{P(OMe)₃}₂{μ-Ph₂PCH(Me)PPh₂} (7), respectively. Addition of dihydrogen to 1 cleanly affords the unsaturated 46-electron cluster Os₃(CO)₈{μ-Ph₂PCH(Me)PPh₂}(μ-H)₂ (8). All the new clusters have been spectroscopically characterized together with single crystal X-ray diffraction studies of 2, 3 and 8.

Original language	English
Article number	114608
Journal	POLYHEDRON
Volume	186
DOIs	https://doi.org/10.1016/j.poly.2020.114608
Publication status	Published - 1 Aug 2020

Keywords

1,1′-Bis(diphenylphosphino)ethane
Dihydrogen (H)
Phosphine
Phosphite
Triosmium clusters

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@article{22e57f1e22494832917675ddd35aaa06,

title = "Reactions of the lightly-stabilized triosmium cluster Os3(CO)8{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) with two-electron donor ligands",

abstract = "Reactions of the lightly-stabilized Os3(CO)8{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (1) with dihydrogen and representative 2-electron donor ligands, PPh3 and P(OMe)3, are described. With PPh3, the phosphine-adduct Os3(CO)8(PPh3){μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (2) is initially formed but this reacts further via three separate pathways: adding a second equivalent of PPh3 to yield Os3(CO)8(PPh3)2{μ-Ph2PCH(Me)PPh2} (5), losing a CO ligand with concomitant phosphine migration to afford Os3(CO)7(PPh3){μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (3) or adding a CO ligand to yield Os3(CO)9(PPh3){μ-Ph2PCH(Me)PPh2} (4). In contrast, reaction with P(OMe)3 leads to the simple stepwise formation of the mono- and bis-phosphite adducts, Os3(CO)8{P(OMe)3}{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (6) and Os3(CO)8{P(OMe)3}2{μ-Ph2PCH(Me)PPh2} (7), respectively. Addition of dihydrogen to 1 cleanly affords the unsaturated 46-electron cluster Os3(CO)8{μ-Ph2PCH(Me)PPh2}(μ-H)2 (8). All the new clusters have been spectroscopically characterized together with single crystal X-ray diffraction studies of 2, 3 and 8.",

keywords = "1,1′-Bis(diphenylphosphino)ethane, Dihydrogen (H), Phosphine, Phosphite, Triosmium clusters",

author = "Sarker, {Jagodish C.} and Saifur Rahman and Shishir Ghosh and Graeme Hogarth and Kabir, {Shariff E.}",

year = "2020",

month = aug,

day = "1",

doi = "10.1016/j.poly.2020.114608",

language = "English",

volume = "186",

journal = "POLYHEDRON",

issn = "0277-5387",

publisher = "PERGAMON-ELSEVIER SCIENCE LTD",

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TY - JOUR

T1 - Reactions of the lightly-stabilized triosmium cluster Os3(CO)8{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) with two-electron donor ligands

AU - Sarker, Jagodish C.

AU - Rahman, Saifur

AU - Ghosh, Shishir

AU - Hogarth, Graeme

AU - Kabir, Shariff E.

PY - 2020/8/1

Y1 - 2020/8/1

N2 - Reactions of the lightly-stabilized Os3(CO)8{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (1) with dihydrogen and representative 2-electron donor ligands, PPh3 and P(OMe)3, are described. With PPh3, the phosphine-adduct Os3(CO)8(PPh3){μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (2) is initially formed but this reacts further via three separate pathways: adding a second equivalent of PPh3 to yield Os3(CO)8(PPh3)2{μ-Ph2PCH(Me)PPh2} (5), losing a CO ligand with concomitant phosphine migration to afford Os3(CO)7(PPh3){μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (3) or adding a CO ligand to yield Os3(CO)9(PPh3){μ-Ph2PCH(Me)PPh2} (4). In contrast, reaction with P(OMe)3 leads to the simple stepwise formation of the mono- and bis-phosphite adducts, Os3(CO)8{P(OMe)3}{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (6) and Os3(CO)8{P(OMe)3}2{μ-Ph2PCH(Me)PPh2} (7), respectively. Addition of dihydrogen to 1 cleanly affords the unsaturated 46-electron cluster Os3(CO)8{μ-Ph2PCH(Me)PPh2}(μ-H)2 (8). All the new clusters have been spectroscopically characterized together with single crystal X-ray diffraction studies of 2, 3 and 8.

AB - Reactions of the lightly-stabilized Os3(CO)8{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (1) with dihydrogen and representative 2-electron donor ligands, PPh3 and P(OMe)3, are described. With PPh3, the phosphine-adduct Os3(CO)8(PPh3){μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (2) is initially formed but this reacts further via three separate pathways: adding a second equivalent of PPh3 to yield Os3(CO)8(PPh3)2{μ-Ph2PCH(Me)PPh2} (5), losing a CO ligand with concomitant phosphine migration to afford Os3(CO)7(PPh3){μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (3) or adding a CO ligand to yield Os3(CO)9(PPh3){μ-Ph2PCH(Me)PPh2} (4). In contrast, reaction with P(OMe)3 leads to the simple stepwise formation of the mono- and bis-phosphite adducts, Os3(CO)8{P(OMe)3}{μ3-Ph2PCH(Me)P(Ph)C6H4}(μ-H) (6) and Os3(CO)8{P(OMe)3}2{μ-Ph2PCH(Me)PPh2} (7), respectively. Addition of dihydrogen to 1 cleanly affords the unsaturated 46-electron cluster Os3(CO)8{μ-Ph2PCH(Me)PPh2}(μ-H)2 (8). All the new clusters have been spectroscopically characterized together with single crystal X-ray diffraction studies of 2, 3 and 8.

KW - 1,1′-Bis(diphenylphosphino)ethane

KW - Dihydrogen (H)

KW - Phosphine

KW - Phosphite

KW - Triosmium clusters

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U2 - 10.1016/j.poly.2020.114608

DO - 10.1016/j.poly.2020.114608

M3 - Article

AN - SCOPUS:85085937256

SN - 0277-5387

VL - 186

JO - POLYHEDRON

JF - POLYHEDRON

M1 - 114608

ER -

Reactions of the lightly-stabilized triosmium cluster Os₃(CO)₈{μ₃-Ph₂PCH(Me)P(Ph)C₆H₄}(μ-H) with two-electron donor ligands

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