The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives

Nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts

Ho Shin Jun Ho Shin, W. Savage, V. J. Murphy, Jeffrey B. Bonanno, D. G. Churchill, G. Parkin

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(CpBut)2Mo} (CpBut = C5H4But), has demonstrated that the η2-acetonitrile ligand in (CpBut)2Mo(η2-MeCN) may be alkylated by RI (R = Me, Et) at nitrogen to give iminoacyl derivatives, [(CpBut)2Mo(η2-MeC=NR)]+, which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (CpBut)2Mo(EPh)H (E = S, Se, Te) have been obtained by reaction of (CpBut)2MoH2 with Ph2E2, and may be alkylated by MeI to give the chalcogenoether adducts [(CpBut)2Mo(PhEMe)H]I. Dynamic NMR studies on [(CpBut)2Mo(PhEMe)H]+ indicate that the barrier to inversion at the chalcogen increases in the sequence S < Se < Te. The oxo complex (CpBut)2MoO reacts with 2 equivalents of Me3SiX (X = Cl, Br, I, O2CMe, O3SMe) to yield (CpBut)2MoX2; for X = CN and NCS, (CpBut)2Mo(OSiMe3)X, the product of reaction with 1 equivalent may be isolated. (CpBut)2Mo(OSiMe3)X (X = CN, NCS) reacts with Me3SiNCS to give the thiocyanate complex (CpBut)2Mo(SCN)X, rather than the isocyanate isomer, (CpBut)2Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include: (CpBut)2MoX2 (X = H, Cl, Br, I, Me, CH2Ph, CH2SiMe3), (CpBut)2MoL (L = CO, C2H4, C2H2, MeCN, PMe3), [(CpBut)2Mo(μ-E)]2, (CpBut)2Mo(η2-E2) and (CpBut)2Mo(EPh)2 (E = S, Se, Te).

Original languageEnglish (US)
Pages (from-to)1732-1753
Number of pages22
JournalJournal of the Chemical Society, Dalton Transactions
Issue number11
StatePublished - 2001
Externally publishedYes

Fingerprint

Chalcogens
Molybdenum
Alkylation
Nitrogen
Ligands
Derivatives
Isocyanates
Carbon Monoxide
Hydrides
Isomers
Nuclear magnetic resonance
Hydrogen
acetonitrile

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{fc8b7f9056f34cab91825506467d58b4,
title = "The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives: Nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts",
abstract = "An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(CpBut)2Mo} (CpBut = C5H4But), has demonstrated that the η2-acetonitrile ligand in (CpBut)2Mo(η2-MeCN) may be alkylated by RI (R = Me, Et) at nitrogen to give iminoacyl derivatives, [(CpBut)2Mo(η2-MeC=NR)]+, which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (CpBut)2Mo(EPh)H (E = S, Se, Te) have been obtained by reaction of (CpBut)2MoH2 with Ph2E2, and may be alkylated by MeI to give the chalcogenoether adducts [(CpBut)2Mo(PhEMe)H]I. Dynamic NMR studies on [(CpBut)2Mo(PhEMe)H]+ indicate that the barrier to inversion at the chalcogen increases in the sequence S < Se < Te. The oxo complex (CpBut)2MoO reacts with 2 equivalents of Me3SiX (X = Cl, Br, I, O2CMe, O3SMe) to yield (CpBut)2MoX2; for X = CN and NCS, (CpBut)2Mo(OSiMe3)X, the product of reaction with 1 equivalent may be isolated. (CpBut)2Mo(OSiMe3)X (X = CN, NCS) reacts with Me3SiNCS to give the thiocyanate complex (CpBut)2Mo(SCN)X, rather than the isocyanate isomer, (CpBut)2Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include: (CpBut)2MoX2 (X = H, Cl, Br, I, Me, CH2Ph, CH2SiMe3), (CpBut)2MoL (L = CO, C2H4, C2H2, MeCN, PMe3), [(CpBut)2Mo(μ-E)]2, (CpBut)2Mo(η2-E2) and (CpBut)2Mo(EPh)2 (E = S, Se, Te).",
author = "{Jun Ho Shin}, {Ho Shin} and W. Savage and Murphy, {V. J.} and Bonanno, {Jeffrey B.} and Churchill, {D. G.} and G. Parkin",
year = "2001",
language = "English (US)",
pages = "1732--1753",
journal = "Journal of the Chemical Society. Dalton Transactions",
issn = "1470-479X",
publisher = "Royal Society of Chemistry",
number = "11",

}

TY - JOUR

T1 - The syntheses, structures and reactivity of bis(tert-butylcyclopentadienyl)molybdenum derivatives

T2 - Nitrogen alkylation of an η2-acetonitrile ligand and influence of the chalcogen on the barrier to inversion of chalcogenoether adducts

AU - Jun Ho Shin, Ho Shin

AU - Savage, W.

AU - Murphy, V. J.

AU - Bonanno, Jeffrey B.

AU - Churchill, D. G.

AU - Parkin, G.

PY - 2001

Y1 - 2001

N2 - An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(CpBut)2Mo} (CpBut = C5H4But), has demonstrated that the η2-acetonitrile ligand in (CpBut)2Mo(η2-MeCN) may be alkylated by RI (R = Me, Et) at nitrogen to give iminoacyl derivatives, [(CpBut)2Mo(η2-MeC=NR)]+, which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (CpBut)2Mo(EPh)H (E = S, Se, Te) have been obtained by reaction of (CpBut)2MoH2 with Ph2E2, and may be alkylated by MeI to give the chalcogenoether adducts [(CpBut)2Mo(PhEMe)H]I. Dynamic NMR studies on [(CpBut)2Mo(PhEMe)H]+ indicate that the barrier to inversion at the chalcogen increases in the sequence S < Se < Te. The oxo complex (CpBut)2MoO reacts with 2 equivalents of Me3SiX (X = Cl, Br, I, O2CMe, O3SMe) to yield (CpBut)2MoX2; for X = CN and NCS, (CpBut)2Mo(OSiMe3)X, the product of reaction with 1 equivalent may be isolated. (CpBut)2Mo(OSiMe3)X (X = CN, NCS) reacts with Me3SiNCS to give the thiocyanate complex (CpBut)2Mo(SCN)X, rather than the isocyanate isomer, (CpBut)2Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include: (CpBut)2MoX2 (X = H, Cl, Br, I, Me, CH2Ph, CH2SiMe3), (CpBut)2MoL (L = CO, C2H4, C2H2, MeCN, PMe3), [(CpBut)2Mo(μ-E)]2, (CpBut)2Mo(η2-E2) and (CpBut)2Mo(EPh)2 (E = S, Se, Te).

AB - An investigation of the chemistry of the tert-butyl-substituted molybdenocene system, {(CpBut)2Mo} (CpBut = C5H4But), has demonstrated that the η2-acetonitrile ligand in (CpBut)2Mo(η2-MeCN) may be alkylated by RI (R = Me, Et) at nitrogen to give iminoacyl derivatives, [(CpBut)2Mo(η2-MeC=NR)]+, which is a new type of reactivity for mononuclear acetonitrile complexes. A series of chalcogenolate-hydride complexes (CpBut)2Mo(EPh)H (E = S, Se, Te) have been obtained by reaction of (CpBut)2MoH2 with Ph2E2, and may be alkylated by MeI to give the chalcogenoether adducts [(CpBut)2Mo(PhEMe)H]I. Dynamic NMR studies on [(CpBut)2Mo(PhEMe)H]+ indicate that the barrier to inversion at the chalcogen increases in the sequence S < Se < Te. The oxo complex (CpBut)2MoO reacts with 2 equivalents of Me3SiX (X = Cl, Br, I, O2CMe, O3SMe) to yield (CpBut)2MoX2; for X = CN and NCS, (CpBut)2Mo(OSiMe3)X, the product of reaction with 1 equivalent may be isolated. (CpBut)2Mo(OSiMe3)X (X = CN, NCS) reacts with Me3SiNCS to give the thiocyanate complex (CpBut)2Mo(SCN)X, rather than the isocyanate isomer, (CpBut)2Mo(NCS)X, thereby indicating that the reactions do not involve a simple metathesis of the Si-NCS bond. Other complexes that are reported include: (CpBut)2MoX2 (X = H, Cl, Br, I, Me, CH2Ph, CH2SiMe3), (CpBut)2MoL (L = CO, C2H4, C2H2, MeCN, PMe3), [(CpBut)2Mo(μ-E)]2, (CpBut)2Mo(η2-E2) and (CpBut)2Mo(EPh)2 (E = S, Se, Te).

UR - http://www.scopus.com/inward/record.url?scp=0035822174&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035822174&partnerID=8YFLogxK

M3 - Article

SP - 1732

EP - 1753

JO - Journal of the Chemical Society. Dalton Transactions

JF - Journal of the Chemical Society. Dalton Transactions

SN - 1470-479X

IS - 11

ER -