Synthesis of carbyne complexes of chromium, molybdenum, and tungsten by formal oxide abstraction from acyl ligands

Gregory A. McDermott; Alison M. Dorries; Andreas Mayr

doi:10.1021/om00148a005

Synthesis of carbyne complexes of chromium, molybdenum, and tungsten by formal oxide abstraction from acyl ligands

Gregory A. McDermott
, Alison M. Dorries
, Andreas Mayr

Chemistry

Princeton University

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

109 Scopus citations

Abstract

Reaction of the acyl metal complexes [NMe₄][M(C(O)R)(CO)₅] (R = C₆H₅, M = Cr, Mo, W; R = CH₃, M = W) with the Lewis acids COCl₂, C₂O₂Cl₂, C₂O₂Br₂, and ClC(O)OCCl₃ in CH₂Cl₂ at low temperatures (≤-78°C) and subsequent warming of the solutions (≤0°C) lead to clean formation of trans-halo(carbyne)tetracarbonylmetal complexes, [M(CR)(X)(CO)₄] (X = Cl, Br). The carbyne complexes [M(CR)X(CO)₄] are transformed into stabilized derivatives [M(CR)X(CO)₂L₂] by the addition of donor ligands (L₂ = (pyridine)₂ (py), tetramethylethylenediamine (tmeda), bipyridine (bpy)). The complex [W-(CPh)(O₂CCF₃)(CO)₂(tmeda)] is prepared in a similar reaction sequence from [NMe₄][W(C(O)Ph)(CO)₅], (CF₃CO)₂O, and tmeda. Reaction of [NMe₄][W(C(O)Ph)(CO)₅] with C₂O₂Br₂ and 1 equiv of PPh₃ gives [W(CPh)Br(CO)₃(PPh₃)]. The bis(pyridine)-substituted complexes [W(CPh)Cl(CO)₂(py)₂] undergo further substitution reactions with PMe₃ and Ph₂PCH₂CH₂PPh₂ (dppe) to give [W(CPh)Cl(CO)₂(PMe₃)₂] and [W(CPh)Cl(CO)₂(dppe)].

Original language	English
Pages (from-to)	925-931
Number of pages	7
Journal	Organometallics
Volume	6
Issue number	5
DOIs	https://doi.org/10.1021/om00148a005
State	Published - 1987

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@article{e5c21b49ed7a4f4995d233376db43733,

title = "Synthesis of carbyne complexes of chromium, molybdenum, and tungsten by formal oxide abstraction from acyl ligands",

abstract = "Reaction of the acyl metal complexes [NMe4][M(C(O)R)(CO)5] (R = C6H5, M = Cr, Mo, W; R = CH3, M = W) with the Lewis acids COCl2, C2O2Cl2, C2O2Br2, and ClC(O)OCCl3 in CH2Cl2 at low temperatures (≤-78°C) and subsequent warming of the solutions (≤0°C) lead to clean formation of trans-halo(carbyne)tetracarbonylmetal complexes, [M(CR)(X)(CO)4] (X = Cl, Br). The carbyne complexes [M(CR)X(CO)4] are transformed into stabilized derivatives [M(CR)X(CO)2L2] by the addition of donor ligands (L2 = (pyridine)2 (py), tetramethylethylenediamine (tmeda), bipyridine (bpy)). The complex [W-(CPh)(O2CCF3)(CO)2(tmeda)] is prepared in a similar reaction sequence from [NMe4][W(C(O)Ph)(CO)5], (CF3CO)2O, and tmeda. Reaction of [NMe4][W(C(O)Ph)(CO)5] with C2O2Br2 and 1 equiv of PPh3 gives [W(CPh)Br(CO)3(PPh3)]. The bis(pyridine)-substituted complexes [W(CPh)Cl(CO)2(py)2] undergo further substitution reactions with PMe3 and Ph2PCH2CH2PPh2 (dppe) to give [W(CPh)Cl(CO)2(PMe3)2] and [W(CPh)Cl(CO)2(dppe)].",

author = "McDermott, \{Gregory A.\} and Dorries, \{Alison M.\} and Andreas Mayr",

year = "1987",

doi = "10.1021/om00148a005",

language = "English",

volume = "6",

pages = "925--931",

journal = "Organometallics",

issn = "0276-7333",

number = "5",

}

TY - JOUR

T1 - Synthesis of carbyne complexes of chromium, molybdenum, and tungsten by formal oxide abstraction from acyl ligands

AU - McDermott, Gregory A.

AU - Dorries, Alison M.

AU - Mayr, Andreas

PY - 1987

Y1 - 1987

N2 - Reaction of the acyl metal complexes [NMe4][M(C(O)R)(CO)5] (R = C6H5, M = Cr, Mo, W; R = CH3, M = W) with the Lewis acids COCl2, C2O2Cl2, C2O2Br2, and ClC(O)OCCl3 in CH2Cl2 at low temperatures (≤-78°C) and subsequent warming of the solutions (≤0°C) lead to clean formation of trans-halo(carbyne)tetracarbonylmetal complexes, [M(CR)(X)(CO)4] (X = Cl, Br). The carbyne complexes [M(CR)X(CO)4] are transformed into stabilized derivatives [M(CR)X(CO)2L2] by the addition of donor ligands (L2 = (pyridine)2 (py), tetramethylethylenediamine (tmeda), bipyridine (bpy)). The complex [W-(CPh)(O2CCF3)(CO)2(tmeda)] is prepared in a similar reaction sequence from [NMe4][W(C(O)Ph)(CO)5], (CF3CO)2O, and tmeda. Reaction of [NMe4][W(C(O)Ph)(CO)5] with C2O2Br2 and 1 equiv of PPh3 gives [W(CPh)Br(CO)3(PPh3)]. The bis(pyridine)-substituted complexes [W(CPh)Cl(CO)2(py)2] undergo further substitution reactions with PMe3 and Ph2PCH2CH2PPh2 (dppe) to give [W(CPh)Cl(CO)2(PMe3)2] and [W(CPh)Cl(CO)2(dppe)].

AB - Reaction of the acyl metal complexes [NMe4][M(C(O)R)(CO)5] (R = C6H5, M = Cr, Mo, W; R = CH3, M = W) with the Lewis acids COCl2, C2O2Cl2, C2O2Br2, and ClC(O)OCCl3 in CH2Cl2 at low temperatures (≤-78°C) and subsequent warming of the solutions (≤0°C) lead to clean formation of trans-halo(carbyne)tetracarbonylmetal complexes, [M(CR)(X)(CO)4] (X = Cl, Br). The carbyne complexes [M(CR)X(CO)4] are transformed into stabilized derivatives [M(CR)X(CO)2L2] by the addition of donor ligands (L2 = (pyridine)2 (py), tetramethylethylenediamine (tmeda), bipyridine (bpy)). The complex [W-(CPh)(O2CCF3)(CO)2(tmeda)] is prepared in a similar reaction sequence from [NMe4][W(C(O)Ph)(CO)5], (CF3CO)2O, and tmeda. Reaction of [NMe4][W(C(O)Ph)(CO)5] with C2O2Br2 and 1 equiv of PPh3 gives [W(CPh)Br(CO)3(PPh3)]. The bis(pyridine)-substituted complexes [W(CPh)Cl(CO)2(py)2] undergo further substitution reactions with PMe3 and Ph2PCH2CH2PPh2 (dppe) to give [W(CPh)Cl(CO)2(PMe3)2] and [W(CPh)Cl(CO)2(dppe)].

UR - https://www.scopus.com/pages/publications/0001250815

U2 - 10.1021/om00148a005

DO - 10.1021/om00148a005

M3 - Article

AN - SCOPUS:0001250815

SN - 0276-7333

VL - 6

SP - 925

EP - 931

JO - Organometallics

JF - Organometallics

IS - 5

ER -

Synthesis of carbyne complexes of chromium, molybdenum, and tungsten by formal oxide abstraction from acyl ligands

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