Synthesis, characterisation and reactivity of the first heptamethylindenyl-molybdenum complexes

Crystal structures of [Mo(CO)(η2≡CMe) 25-C9Me7)]BF4 and [Mo(CO) 23-C3H5)(η5-C9Me7)]

Michael Green, Thomas D. McGrath, Rhodri Ll Thomas, Alan P. Walker

Research output: Contribution to journalArticle

Abstract

The synthesis and characterisation of the first (?5-heptamethylindenyl)molybdenum complexes are reported. Reaction of Li[C9Me7] with Mo(CO)6 in refluxing THF readily forms Li[Mo(CO)3(?5-C9Me7)], which is shown to be a useful precursor in the formation of (carbonyl)(?5-heptamethylindenyl)molybdenum complexes. The compounds [MoI(CO)3(?5-C9Me7)] 3, [Mo(Me)(CO)3(?5-C9Me7)] 4 and [Mo(CO)2(?3-C3H5)(?5-C9Me7)] 5 have been prepared from this intermediate and characterised. Treatment of 3 with AgBF4 and MeC=CMe affords [Mo(CO)(MeC=CMe)2(?5-C9Me7)]BF4 6a; for this and the indenyl analogue, a new route to carbonyl-bis(alkyne)-molybdenum derivatives is demonstrated. Reaction of 3 with T1PF6 in MeCN forms the complex [Mo(MeCN)2(CO)2(?5-C9Me7)]PF6 7. Protonation of 5 in the presence of MeC=CMe, or reaction of 7 with the same acetylene, also yields 6 with appropriate counter anions. Single crystal X-ray diffraction studies of compounds 5 and 6a are reported.

Original languageEnglish
Pages (from-to)61-70
Number of pages10
JournalJournal of Organometallic Chemistry
Volume532
Issue number1-2
DOIs
Publication statusPublished - 1 Apr 1997

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Molybdenum
Crystal structure
Acetylene
Alkynes
Protonation
Anions
Single crystals
Derivatives
X ray diffraction

Keywords

  • Alkyne
  • Carbonyl
  • Crystal structure
  • Heptamethylindenyl
  • Indenyl
  • Molybdenum
  • Permethylindenyl

Cite this

@article{99ecb5f4eb3b4a5582b19017f9e888bc,
title = "Synthesis, characterisation and reactivity of the first heptamethylindenyl-molybdenum complexes: Crystal structures of [Mo(CO)(η2≡CMe) 2(η5-C9Me7)]BF4 and [Mo(CO) 2(η3-C3H5)(η5-C9Me7)]",
abstract = "The synthesis and characterisation of the first (?5-heptamethylindenyl)molybdenum complexes are reported. Reaction of Li[C9Me7] with Mo(CO)6 in refluxing THF readily forms Li[Mo(CO)3(?5-C9Me7)], which is shown to be a useful precursor in the formation of (carbonyl)(?5-heptamethylindenyl)molybdenum complexes. The compounds [MoI(CO)3(?5-C9Me7)] 3, [Mo(Me)(CO)3(?5-C9Me7)] 4 and [Mo(CO)2(?3-C3H5)(?5-C9Me7)] 5 have been prepared from this intermediate and characterised. Treatment of 3 with AgBF4 and MeC=CMe affords [Mo(CO)(MeC=CMe)2(?5-C9Me7)]BF4 6a; for this and the indenyl analogue, a new route to carbonyl-bis(alkyne)-molybdenum derivatives is demonstrated. Reaction of 3 with T1PF6 in MeCN forms the complex [Mo(MeCN)2(CO)2(?5-C9Me7)]PF6 7. Protonation of 5 in the presence of MeC=CMe, or reaction of 7 with the same acetylene, also yields 6 with appropriate counter anions. Single crystal X-ray diffraction studies of compounds 5 and 6a are reported.",
keywords = "Alkyne, Carbonyl, Crystal structure, Heptamethylindenyl, Indenyl, Molybdenum, Permethylindenyl",
author = "Michael Green and McGrath, {Thomas D.} and Thomas, {Rhodri Ll} and Walker, {Alan P.}",
year = "1997",
month = "4",
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language = "English",
volume = "532",
pages = "61--70",
journal = "Journal of Organometallic Chemistry",
issn = "0022-328X",
publisher = "Elsevier",
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Synthesis, characterisation and reactivity of the first heptamethylindenyl-molybdenum complexes : Crystal structures of [Mo(CO)(η2≡CMe) 25-C9Me7)]BF4 and [Mo(CO) 23-C3H5)(η5-C9Me7)]. / Green, Michael; McGrath, Thomas D.; Thomas, Rhodri Ll; Walker, Alan P.

In: Journal of Organometallic Chemistry, Vol. 532, No. 1-2, 01.04.1997, p. 61-70.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, characterisation and reactivity of the first heptamethylindenyl-molybdenum complexes

T2 - Crystal structures of [Mo(CO)(η2≡CMe) 2(η5-C9Me7)]BF4 and [Mo(CO) 2(η3-C3H5)(η5-C9Me7)]

AU - Green, Michael

AU - McGrath, Thomas D.

AU - Thomas, Rhodri Ll

AU - Walker, Alan P.

PY - 1997/4/1

Y1 - 1997/4/1

N2 - The synthesis and characterisation of the first (?5-heptamethylindenyl)molybdenum complexes are reported. Reaction of Li[C9Me7] with Mo(CO)6 in refluxing THF readily forms Li[Mo(CO)3(?5-C9Me7)], which is shown to be a useful precursor in the formation of (carbonyl)(?5-heptamethylindenyl)molybdenum complexes. The compounds [MoI(CO)3(?5-C9Me7)] 3, [Mo(Me)(CO)3(?5-C9Me7)] 4 and [Mo(CO)2(?3-C3H5)(?5-C9Me7)] 5 have been prepared from this intermediate and characterised. Treatment of 3 with AgBF4 and MeC=CMe affords [Mo(CO)(MeC=CMe)2(?5-C9Me7)]BF4 6a; for this and the indenyl analogue, a new route to carbonyl-bis(alkyne)-molybdenum derivatives is demonstrated. Reaction of 3 with T1PF6 in MeCN forms the complex [Mo(MeCN)2(CO)2(?5-C9Me7)]PF6 7. Protonation of 5 in the presence of MeC=CMe, or reaction of 7 with the same acetylene, also yields 6 with appropriate counter anions. Single crystal X-ray diffraction studies of compounds 5 and 6a are reported.

AB - The synthesis and characterisation of the first (?5-heptamethylindenyl)molybdenum complexes are reported. Reaction of Li[C9Me7] with Mo(CO)6 in refluxing THF readily forms Li[Mo(CO)3(?5-C9Me7)], which is shown to be a useful precursor in the formation of (carbonyl)(?5-heptamethylindenyl)molybdenum complexes. The compounds [MoI(CO)3(?5-C9Me7)] 3, [Mo(Me)(CO)3(?5-C9Me7)] 4 and [Mo(CO)2(?3-C3H5)(?5-C9Me7)] 5 have been prepared from this intermediate and characterised. Treatment of 3 with AgBF4 and MeC=CMe affords [Mo(CO)(MeC=CMe)2(?5-C9Me7)]BF4 6a; for this and the indenyl analogue, a new route to carbonyl-bis(alkyne)-molybdenum derivatives is demonstrated. Reaction of 3 with T1PF6 in MeCN forms the complex [Mo(MeCN)2(CO)2(?5-C9Me7)]PF6 7. Protonation of 5 in the presence of MeC=CMe, or reaction of 7 with the same acetylene, also yields 6 with appropriate counter anions. Single crystal X-ray diffraction studies of compounds 5 and 6a are reported.

KW - Alkyne

KW - Carbonyl

KW - Crystal structure

KW - Heptamethylindenyl

KW - Indenyl

KW - Molybdenum

KW - Permethylindenyl

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U2 - 10.1016/S0022-328X(96)06751-4

DO - 10.1016/S0022-328X(96)06751-4

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VL - 532

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EP - 70

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

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