Reactivity of platinum and palladium α-ketoacyl complexes toward olefins and acetylenes

William M. Vetter; Ayusman Sen

doi:10.1016/0022-328X(89)85373-2

Reactivity of platinum and palladium α-ketoacyl complexes toward olefins and acetylenes

William M. Vetter
, Ayusman Sen

Chemistry

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

27 Scopus citations

Abstract

The α-ketoacyl complexes trans-M(PPh₃)₂(Cl)(COCO₂R) (M = Pd, R = (CH₂)_nCHCH₂, n = 2, 3, 4, R = (CH₂)₂CCMe; M = Pt, R = (CH₂)_nCHCH₂, n = 2, 3, 4, R = (CH₂)₂CCMe) were prepared by treating M(PPh₃)₄ with ROCOCOCl. Attempts to insert the pendant olefin or acetylene into the α-ketoacyl-to-metal bond through heating failed, since CO deinsertion to form corresponding acyl complexes was predominant. Reaction of [trans-Pt(PPh₃)₂(NCMe)(COCOR)]BF₄ (R = Me, Ph) with norbornylene resulted in the deinsertion of CO from the α-ketoacyl ligand and the formation of [cis-Pt(PPh₃)₂(C₇H₁₀COR)]BF₄, an insertion of norbornylene into the corresponding acyl ligand.

Original language	English (US)
Pages (from-to)	485-491
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	378
Issue number	3
DOIs	https://doi.org/10.1016/0022-328X(89)85373-2
State	Published - Dec 12 1989

All Science Journal Classification (ASJC) codes

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

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10.1016/0022-328X(89)85373-2

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@article{5216ffca01464b9782138a8470bb3784,

title = "Reactivity of platinum and palladium α-ketoacyl complexes toward olefins and acetylenes",

abstract = "The α-ketoacyl complexes trans-M(PPh3)2(Cl)(COCO2R) (M = Pd, R = (CH2)nCHCH2, n = 2, 3, 4, R = (CH2)2CCMe; M = Pt, R = (CH2)nCHCH2, n = 2, 3, 4, R = (CH2)2CCMe) were prepared by treating M(PPh3)4 with ROCOCOCl. Attempts to insert the pendant olefin or acetylene into the α-ketoacyl-to-metal bond through heating failed, since CO deinsertion to form corresponding acyl complexes was predominant. Reaction of [trans-Pt(PPh3)2(NCMe)(COCOR)]BF4 (R = Me, Ph) with norbornylene resulted in the deinsertion of CO from the α-ketoacyl ligand and the formation of [cis-Pt(PPh3)2(C7H10COR)]BF4, an insertion of norbornylene into the corresponding acyl ligand.",

author = "Vetter, \{William M.\} and Ayusman Sen",

note = "Funding Information: This research was supported by a grant from the U.S. Department of Energy, Office of Basic Energy Sciences (DE-FG02-84ER13295). We also wish to thank Johnson Matthey for generousl oans of noble metal salts.",

year = "1989",

month = dec,

day = "12",

doi = "10.1016/0022-328X(89)85373-2",

language = "English (US)",

volume = "378",

pages = "485--491",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "3",

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TY - JOUR

T1 - Reactivity of platinum and palladium α-ketoacyl complexes toward olefins and acetylenes

AU - Vetter, William M.

AU - Sen, Ayusman

N1 - Funding Information: This research was supported by a grant from the U.S. Department of Energy, Office of Basic Energy Sciences (DE-FG02-84ER13295). We also wish to thank Johnson Matthey for generousl oans of noble metal salts.

PY - 1989/12/12

Y1 - 1989/12/12

N2 - The α-ketoacyl complexes trans-M(PPh3)2(Cl)(COCO2R) (M = Pd, R = (CH2)nCHCH2, n = 2, 3, 4, R = (CH2)2CCMe; M = Pt, R = (CH2)nCHCH2, n = 2, 3, 4, R = (CH2)2CCMe) were prepared by treating M(PPh3)4 with ROCOCOCl. Attempts to insert the pendant olefin or acetylene into the α-ketoacyl-to-metal bond through heating failed, since CO deinsertion to form corresponding acyl complexes was predominant. Reaction of [trans-Pt(PPh3)2(NCMe)(COCOR)]BF4 (R = Me, Ph) with norbornylene resulted in the deinsertion of CO from the α-ketoacyl ligand and the formation of [cis-Pt(PPh3)2(C7H10COR)]BF4, an insertion of norbornylene into the corresponding acyl ligand.

AB - The α-ketoacyl complexes trans-M(PPh3)2(Cl)(COCO2R) (M = Pd, R = (CH2)nCHCH2, n = 2, 3, 4, R = (CH2)2CCMe; M = Pt, R = (CH2)nCHCH2, n = 2, 3, 4, R = (CH2)2CCMe) were prepared by treating M(PPh3)4 with ROCOCOCl. Attempts to insert the pendant olefin or acetylene into the α-ketoacyl-to-metal bond through heating failed, since CO deinsertion to form corresponding acyl complexes was predominant. Reaction of [trans-Pt(PPh3)2(NCMe)(COCOR)]BF4 (R = Me, Ph) with norbornylene resulted in the deinsertion of CO from the α-ketoacyl ligand and the formation of [cis-Pt(PPh3)2(C7H10COR)]BF4, an insertion of norbornylene into the corresponding acyl ligand.

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U2 - 10.1016/0022-328X(89)85373-2

DO - 10.1016/0022-328X(89)85373-2

M3 - Article

AN - SCOPUS:0010950408

SN - 0022-328X

VL - 378

SP - 485

EP - 491

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 3

ER -

Reactivity of platinum and palladium α-ketoacyl complexes toward olefins and acetylenes

Abstract

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