Syntheses and structures of six and seven-coordinate diene complexes of molybdenum and tungsten(II). The crystal and molecular structures of [WBr2(CO)2(PMePh2)(norbornadiene)] and [WBr2(CO)(NCCH=CH2)(norbornadiene)]

Jack L. Davidson; Heiko Richtzenhein; B. J S Thiebaut; Kai Landskron; Georgina M. Rosair

Syntheses and structures of six and seven-coordinate diene complexes of molybdenum and tungsten(II). The crystal and molecular structures of [WBr₂(CO)₂(PMePh₂)(norbornadiene)] and [WBr₂(CO)(NCCH=CH₂)(norbornadiene)]

Jack L. Davidson, Heiko Richtzenhein, B. J S Thiebaut, Kai Landskron, Georgina M. Rosair

School of Engineering & Physical Sciences

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

9 Citations (Scopus)

Abstract

Reactions of [WI₂(CO)₃(NCMe)₂] with norbornadiene (NBD) and 1,5-cycloctadiene (COD) give six-coordinate dicarbonyls [WI₂(CO)₂(NBD)] and [WI₂(CO)₂(COD)], respectively. The related dibromo complex [WBr₂(CO)₂(NBD)] reacts with tertiary phosphines L to give unstable seven-coordinate adducts [WBr₂(CO)₂(L)(NBD)] (L=PPh₃, PMePh₂, PEt₃), which in the case of L=PMePh₂ was shown to undergo CO loss to give the six-coordinate derivative [WBr₂(CO)(PMePh₂)(NBD)]. X-ray diffraction studies of [WBr₂(CO)₂(PMePh₂)(NBD)] reveal a seven-coordinate structure (distorted pentagonal bipyramid) with the diene C=C bonds on the pentagonal plane lying approximately parallel to the W-CO axes. Reactions of [WBr₂(CO)₂(NBD)] with organonitriles NCR at room temperature afford CO substitution products (R=Me, Prⁱ, Ph, C₆H₄Me-4, CH=CH₂) directly with no evidence for seven-coordinate intermediates. [WBr₂(CO)₂(COD)] and acetonitrile similarly give [WBr₂(CO)(NCMe)(COD)]. X-ray diffraction studies of [WBr₂(CO)(NCCH=CH₂)(NBD)] confirmed a distorted octahedral structure where the carbonyl lies trans to the acrylonitrile ligand. © 1999 Elsevier Science S.A.

Original language	English
Pages (from-to)	168-179
Number of pages	12
Journal	Journal of Organometallic Chemistry
Volume	592
Issue number	2
Publication status	Published - 25 Dec 1999

Keywords

Crystal structures
Norbornadiene
Seven coordination
Six coordination
Synthesis
Tungsten

Fingerprint

Dive into the research topics of 'Syntheses and structures of six and seven-coordinate diene complexes of molybdenum and tungsten(II). The crystal and molecular structures of [WBr₂(CO)₂(PMePh₂)(norbornadiene)] and [WBr₂(CO)(NCCH=CH₂)(norbornadiene)]'. Together they form a unique fingerprint.

Cite this

@article{4eaa78200a4940a783122557c488de86,

title = "Syntheses and structures of six and seven-coordinate diene complexes of molybdenum and tungsten(II). The crystal and molecular structures of [WBr2(CO)2(PMePh2)(norbornadiene)] and [WBr2(CO)(NCCH=CH2)(norbornadiene)]",

abstract = "Reactions of [WI2(CO)3(NCMe)2] with norbornadiene (NBD) and 1,5-cycloctadiene (COD) give six-coordinate dicarbonyls [WI2(CO)2(NBD)] and [WI2(CO)2(COD)], respectively. The related dibromo complex [WBr2(CO)2(NBD)] reacts with tertiary phosphines L to give unstable seven-coordinate adducts [WBr2(CO)2(L)(NBD)] (L=PPh3, PMePh2, PEt3), which in the case of L=PMePh2 was shown to undergo CO loss to give the six-coordinate derivative [WBr2(CO)(PMePh2)(NBD)]. X-ray diffraction studies of [WBr2(CO)2(PMePh2)(NBD)] reveal a seven-coordinate structure (distorted pentagonal bipyramid) with the diene C=C bonds on the pentagonal plane lying approximately parallel to the W-CO axes. Reactions of [WBr2(CO)2(NBD)] with organonitriles NCR at room temperature afford CO substitution products (R=Me, Pri, Ph, C6H4Me-4, CH=CH2) directly with no evidence for seven-coordinate intermediates. [WBr2(CO)2(COD)] and acetonitrile similarly give [WBr2(CO)(NCMe)(COD)]. X-ray diffraction studies of [WBr2(CO)(NCCH=CH2)(NBD)] confirmed a distorted octahedral structure where the carbonyl lies trans to the acrylonitrile ligand. {\textcopyright} 1999 Elsevier Science S.A.",

keywords = "Crystal structures, Norbornadiene, Seven coordination, Six coordination, Synthesis, Tungsten",

author = "Davidson, {Jack L.} and Heiko Richtzenhein and Thiebaut, {B. J S} and Kai Landskron and Rosair, {Georgina M.}",

year = "1999",

month = dec,

day = "25",

language = "English",

volume = "592",

pages = "168--179",

journal = "Journal of Organometallic Chemistry",

publisher = "Elsevier",

number = "2",

}

Syntheses and structures of six and seven-coordinate diene complexes of molybdenum and tungsten(II). The crystal and molecular structures of [WBr₂(CO)₂(PMePh₂)(norbornadiene)] and [WBr₂(CO)(NCCH=CH₂)(norbornadiene)]. / Davidson, Jack L.; Richtzenhein, Heiko; Thiebaut, B. J S et al.
In: Journal of Organometallic Chemistry, Vol. 592, No. 2, 25.12.1999, p. 168-179.

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

TY - JOUR

T1 - Syntheses and structures of six and seven-coordinate diene complexes of molybdenum and tungsten(II). The crystal and molecular structures of [WBr2(CO)2(PMePh2)(norbornadiene)] and [WBr2(CO)(NCCH=CH2)(norbornadiene)]

AU - Davidson, Jack L.

AU - Richtzenhein, Heiko

AU - Thiebaut, B. J S

AU - Landskron, Kai

AU - Rosair, Georgina M.

PY - 1999/12/25

Y1 - 1999/12/25

N2 - Reactions of [WI2(CO)3(NCMe)2] with norbornadiene (NBD) and 1,5-cycloctadiene (COD) give six-coordinate dicarbonyls [WI2(CO)2(NBD)] and [WI2(CO)2(COD)], respectively. The related dibromo complex [WBr2(CO)2(NBD)] reacts with tertiary phosphines L to give unstable seven-coordinate adducts [WBr2(CO)2(L)(NBD)] (L=PPh3, PMePh2, PEt3), which in the case of L=PMePh2 was shown to undergo CO loss to give the six-coordinate derivative [WBr2(CO)(PMePh2)(NBD)]. X-ray diffraction studies of [WBr2(CO)2(PMePh2)(NBD)] reveal a seven-coordinate structure (distorted pentagonal bipyramid) with the diene C=C bonds on the pentagonal plane lying approximately parallel to the W-CO axes. Reactions of [WBr2(CO)2(NBD)] with organonitriles NCR at room temperature afford CO substitution products (R=Me, Pri, Ph, C6H4Me-4, CH=CH2) directly with no evidence for seven-coordinate intermediates. [WBr2(CO)2(COD)] and acetonitrile similarly give [WBr2(CO)(NCMe)(COD)]. X-ray diffraction studies of [WBr2(CO)(NCCH=CH2)(NBD)] confirmed a distorted octahedral structure where the carbonyl lies trans to the acrylonitrile ligand. © 1999 Elsevier Science S.A.

AB - Reactions of [WI2(CO)3(NCMe)2] with norbornadiene (NBD) and 1,5-cycloctadiene (COD) give six-coordinate dicarbonyls [WI2(CO)2(NBD)] and [WI2(CO)2(COD)], respectively. The related dibromo complex [WBr2(CO)2(NBD)] reacts with tertiary phosphines L to give unstable seven-coordinate adducts [WBr2(CO)2(L)(NBD)] (L=PPh3, PMePh2, PEt3), which in the case of L=PMePh2 was shown to undergo CO loss to give the six-coordinate derivative [WBr2(CO)(PMePh2)(NBD)]. X-ray diffraction studies of [WBr2(CO)2(PMePh2)(NBD)] reveal a seven-coordinate structure (distorted pentagonal bipyramid) with the diene C=C bonds on the pentagonal plane lying approximately parallel to the W-CO axes. Reactions of [WBr2(CO)2(NBD)] with organonitriles NCR at room temperature afford CO substitution products (R=Me, Pri, Ph, C6H4Me-4, CH=CH2) directly with no evidence for seven-coordinate intermediates. [WBr2(CO)2(COD)] and acetonitrile similarly give [WBr2(CO)(NCMe)(COD)]. X-ray diffraction studies of [WBr2(CO)(NCCH=CH2)(NBD)] confirmed a distorted octahedral structure where the carbonyl lies trans to the acrylonitrile ligand. © 1999 Elsevier Science S.A.

KW - Crystal structures

KW - Norbornadiene

KW - Seven coordination

KW - Six coordination

KW - Synthesis

KW - Tungsten

UR - http://www.scopus.com/inward/record.url?scp=0000418403&partnerID=8YFLogxK

M3 - Article

VL - 592

SP - 168

EP - 179

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 2

ER -