Fischer-type alkylidyne tungsten complexes containing strong π donor ligands

Andreas Mayr; Tsung Yi Lee

doi:10.1016/s0020-1693(96)05306-6

Fischer-type alkylidyne tungsten complexes containing strong π donor ligands

Andreas Mayr
, Tsung Yi Lee

Chemistry

Stony Brook University

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

6 Scopus citations

Abstract

Reaction of [W(CPh)Cl(CO)(PMe₃)₃] (1), with NaNC₄H₄, NaNC₈H₆, NaOC₆H₅ and NaSR (R = CMe₃, C₆H₁₁) in THF affords the alkylidyne tungsten complexes [W(CPh)X(CO) (PMe₃)₃] (2a-e), containing pyrrolide, indolide, phenoxide and alkylsulfide ligands, X, respectively. The π donor ligands X occupy the coordination site trans to the alkylidyne ligand. The anionic complexes [NEt₄][W(CPh)X₂(CO)(PMe₃)₂] ((3a) X = NC₄H₄), ((3b) X = NC₈H₆), form upon reaction of 1 with 2 equiv. of NaNC₄H₄ and NaNC₈H₆ in THF, followed by metathesis with NEt₄Cl in CH₂Cl₂. Reaction of 1 with the sodium salt of pyrrole-2-carboxaldehyde methylimine affords [W(CPh)(NC₄H₃-CHNMe-2)(CO)(PMe₃)₂] (4). The solid state structures of complexes 2a and 2e were determined by X-ray crystallography. Complex 2d reacts in THF solution with carbon monoxide to afford cis-[W(CPh)(SCMe₃)(CO)₂(PMe₃)₂] (6). In contrast, the analogous bromo complex [W(CPh)Br(CO)(PMe₃)₃] (7) gives under the same conditions an equilibrium mixture of 7 and trans-[W(CPh)Br(CO)₂(PMe₃)₂].

Original language	English
Pages (from-to)	131-139
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	252
Issue number	1-2
DOIs	https://doi.org/10.1016/s0020-1693(96)05306-6
State	Published - Nov 1 1996

Keywords

Alkylidyne complexes
Crystal structures
Tungsten complexes
π donor ligand complexes

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10.1016/s0020-1693(96)05306-6

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@article{13c83fc1fa354712a305ba24f3a8eb8a,

title = "Fischer-type alkylidyne tungsten complexes containing strong π donor ligands",

abstract = "Reaction of [W(CPh)Cl(CO)(PMe3)3] (1), with NaNC4H4, NaNC8H6, NaOC6H5 and NaSR (R = CMe3, C6H11) in THF affords the alkylidyne tungsten complexes [W(CPh)X(CO) (PMe3)3] (2a-e), containing pyrrolide, indolide, phenoxide and alkylsulfide ligands, X, respectively. The π donor ligands X occupy the coordination site trans to the alkylidyne ligand. The anionic complexes [NEt4][W(CPh)X2(CO)(PMe3)2] ((3a) X = NC4H4), ((3b) X = NC8H6), form upon reaction of 1 with 2 equiv. of NaNC4H4 and NaNC8H6 in THF, followed by metathesis with NEt4Cl in CH2Cl2. Reaction of 1 with the sodium salt of pyrrole-2-carboxaldehyde methylimine affords [W(CPh)(NC4H3-CHNMe-2)(CO)(PMe3)2] (4). The solid state structures of complexes 2a and 2e were determined by X-ray crystallography. Complex 2d reacts in THF solution with carbon monoxide to afford cis-[W(CPh)(SCMe3)(CO)2(PMe3)2] (6). In contrast, the analogous bromo complex [W(CPh)Br(CO)(PMe3)3] (7) gives under the same conditions an equilibrium mixture of 7 and trans-[W(CPh)Br(CO)2(PMe3)2].",

keywords = "Alkylidyne complexes, Crystal structures, Tungsten complexes, π donor ligand complexes",

author = "Andreas Mayr and Lee, \{Tsung Yi\}",

year = "1996",

month = nov,

day = "1",

doi = "10.1016/s0020-1693(96)05306-6",

language = "English",

volume = "252",

pages = "131--139",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

number = "1-2",

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TY - JOUR

T1 - Fischer-type alkylidyne tungsten complexes containing strong π donor ligands

AU - Mayr, Andreas

AU - Lee, Tsung Yi

PY - 1996/11/1

Y1 - 1996/11/1

N2 - Reaction of [W(CPh)Cl(CO)(PMe3)3] (1), with NaNC4H4, NaNC8H6, NaOC6H5 and NaSR (R = CMe3, C6H11) in THF affords the alkylidyne tungsten complexes [W(CPh)X(CO) (PMe3)3] (2a-e), containing pyrrolide, indolide, phenoxide and alkylsulfide ligands, X, respectively. The π donor ligands X occupy the coordination site trans to the alkylidyne ligand. The anionic complexes [NEt4][W(CPh)X2(CO)(PMe3)2] ((3a) X = NC4H4), ((3b) X = NC8H6), form upon reaction of 1 with 2 equiv. of NaNC4H4 and NaNC8H6 in THF, followed by metathesis with NEt4Cl in CH2Cl2. Reaction of 1 with the sodium salt of pyrrole-2-carboxaldehyde methylimine affords [W(CPh)(NC4H3-CHNMe-2)(CO)(PMe3)2] (4). The solid state structures of complexes 2a and 2e were determined by X-ray crystallography. Complex 2d reacts in THF solution with carbon monoxide to afford cis-[W(CPh)(SCMe3)(CO)2(PMe3)2] (6). In contrast, the analogous bromo complex [W(CPh)Br(CO)(PMe3)3] (7) gives under the same conditions an equilibrium mixture of 7 and trans-[W(CPh)Br(CO)2(PMe3)2].

AB - Reaction of [W(CPh)Cl(CO)(PMe3)3] (1), with NaNC4H4, NaNC8H6, NaOC6H5 and NaSR (R = CMe3, C6H11) in THF affords the alkylidyne tungsten complexes [W(CPh)X(CO) (PMe3)3] (2a-e), containing pyrrolide, indolide, phenoxide and alkylsulfide ligands, X, respectively. The π donor ligands X occupy the coordination site trans to the alkylidyne ligand. The anionic complexes [NEt4][W(CPh)X2(CO)(PMe3)2] ((3a) X = NC4H4), ((3b) X = NC8H6), form upon reaction of 1 with 2 equiv. of NaNC4H4 and NaNC8H6 in THF, followed by metathesis with NEt4Cl in CH2Cl2. Reaction of 1 with the sodium salt of pyrrole-2-carboxaldehyde methylimine affords [W(CPh)(NC4H3-CHNMe-2)(CO)(PMe3)2] (4). The solid state structures of complexes 2a and 2e were determined by X-ray crystallography. Complex 2d reacts in THF solution with carbon monoxide to afford cis-[W(CPh)(SCMe3)(CO)2(PMe3)2] (6). In contrast, the analogous bromo complex [W(CPh)Br(CO)(PMe3)3] (7) gives under the same conditions an equilibrium mixture of 7 and trans-[W(CPh)Br(CO)2(PMe3)2].

KW - Alkylidyne complexes

KW - Crystal structures

KW - Tungsten complexes

KW - π donor ligand complexes

UR - https://www.scopus.com/pages/publications/0001543693

U2 - 10.1016/s0020-1693(96)05306-6

DO - 10.1016/s0020-1693(96)05306-6

M3 - Article

AN - SCOPUS:0001543693

SN - 0020-1693

VL - 252

SP - 131

EP - 139

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

IS - 1-2

ER -

Fischer-type alkylidyne tungsten complexes containing strong π donor ligands

Abstract

Keywords

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