Synthesis and structures of rac-Me2Si(η5-1-indenyl)2Hf(NMe 2)2 and {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}Hf(NMe2)2

Joseph N. Christopher; Richard F. Jordan; Jeffrey L. Petersen; Victor G. Young

doi:10.1021/om970242g

Synthesis and structures of rac-Me₂Si(η⁵-1-indenyl)₂Hf(NMe ₂)₂ and {Me₂Si(η⁵-1-indenyl)(η ³-2-indenyl)}Hf(NMe₂)₂

Joseph N. Christopher, Richard F. Jordan, Jeffrey L. Petersen, Victor G. Young

Chemistry (Twin Cities)

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

36 Scopus citations

Abstract

The amine elimination reaction of Me₂Si(1-indenyl)₂ (1, (SBI)H₂) and Hf(NMe₂)₄ (2) affords rac-Me₂Si(η⁵-1-indenyl)₂Hf(NMe ₂)₂ (rac-3, rac-(SBI)Hf(NMe₂)₂) in 20% isolated yield. This reaction proceeds by initial formation of a mono(indenyl) intermediate, (η⁵-C₉H₆SiMe₂C₉H ₇)-Hf(NMe₂)₃ (4), which reacts reversibly with a second equivalent of 2 to form a binuclear complex, {μ-η⁵:η⁵-Me₂Si(1-indenyl) ₂}{Hf(NMe₂)₃}₂ (5), and undergoes reversible intramolecular amine elimination to form rac-3 and meso-3. The novel C₁-symmetric ansametallocene {Me₂Si(η⁵-1-indenyl)(η ₃-2-indenyl)}Hf(NMe₂)₂ (6), in which one of the indenyl groups is bridged through the 2-position, is observed as a side product in the synthesis of 3. Complex 6 has been prepared in 21% isolated yield by thermolysis of 4 (or mixtures of 1 and 2) at 160 °C and can be converted to {Me₂Si(η⁵-1-indenyl)(η ³-2-indenyl)}HfMe₂ (7, 100% NMR) by reaction with AlMe₃. The molecular structures of rac-3 and 6 have been determined by X-ray crystallography.

Original language	English (US)
Pages (from-to)	3044-3050
Number of pages	7
Journal	Organometallics
Volume	16
Issue number	13
DOIs	https://doi.org/10.1021/om970242g
State	Published - Jun 24 1997

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@article{37124767e9df4a1b98f9c040b4604f3f,

title = "Synthesis and structures of rac-Me2Si(η5-1-indenyl)2Hf(NMe 2)2 and {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}Hf(NMe2)2",

abstract = "The amine elimination reaction of Me2Si(1-indenyl)2 (1, (SBI)H2) and Hf(NMe2)4 (2) affords rac-Me2Si(η5-1-indenyl)2Hf(NMe 2)2 (rac-3, rac-(SBI)Hf(NMe2)2) in 20% isolated yield. This reaction proceeds by initial formation of a mono(indenyl) intermediate, (η5-C9H6SiMe2C9H 7)-Hf(NMe2)3 (4), which reacts reversibly with a second equivalent of 2 to form a binuclear complex, {μ-η5:η5-Me2Si(1-indenyl) 2}{Hf(NMe2)3}2 (5), and undergoes reversible intramolecular amine elimination to form rac-3 and meso-3. The novel C1-symmetric ansametallocene {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}Hf(NMe2)2 (6), in which one of the indenyl groups is bridged through the 2-position, is observed as a side product in the synthesis of 3. Complex 6 has been prepared in 21% isolated yield by thermolysis of 4 (or mixtures of 1 and 2) at 160 °C and can be converted to {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}HfMe2 (7, 100% NMR) by reaction with AlMe3. The molecular structures of rac-3 and 6 have been determined by X-ray crystallography.",

author = "Christopher, {Joseph N.} and Jordan, {Richard F.} and Petersen, {Jeffrey L.} and Young, {Victor G.}",

year = "1997",

month = jun,

day = "24",

doi = "10.1021/om970242g",

language = "English (US)",

volume = "16",

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journal = "Organometallics",

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T1 - Synthesis and structures of rac-Me2Si(η5-1-indenyl)2Hf(NMe 2)2 and {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}Hf(NMe2)2

AU - Christopher, Joseph N.

AU - Jordan, Richard F.

AU - Petersen, Jeffrey L.

AU - Young, Victor G.

PY - 1997/6/24

Y1 - 1997/6/24

N2 - The amine elimination reaction of Me2Si(1-indenyl)2 (1, (SBI)H2) and Hf(NMe2)4 (2) affords rac-Me2Si(η5-1-indenyl)2Hf(NMe 2)2 (rac-3, rac-(SBI)Hf(NMe2)2) in 20% isolated yield. This reaction proceeds by initial formation of a mono(indenyl) intermediate, (η5-C9H6SiMe2C9H 7)-Hf(NMe2)3 (4), which reacts reversibly with a second equivalent of 2 to form a binuclear complex, {μ-η5:η5-Me2Si(1-indenyl) 2}{Hf(NMe2)3}2 (5), and undergoes reversible intramolecular amine elimination to form rac-3 and meso-3. The novel C1-symmetric ansametallocene {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}Hf(NMe2)2 (6), in which one of the indenyl groups is bridged through the 2-position, is observed as a side product in the synthesis of 3. Complex 6 has been prepared in 21% isolated yield by thermolysis of 4 (or mixtures of 1 and 2) at 160 °C and can be converted to {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}HfMe2 (7, 100% NMR) by reaction with AlMe3. The molecular structures of rac-3 and 6 have been determined by X-ray crystallography.

AB - The amine elimination reaction of Me2Si(1-indenyl)2 (1, (SBI)H2) and Hf(NMe2)4 (2) affords rac-Me2Si(η5-1-indenyl)2Hf(NMe 2)2 (rac-3, rac-(SBI)Hf(NMe2)2) in 20% isolated yield. This reaction proceeds by initial formation of a mono(indenyl) intermediate, (η5-C9H6SiMe2C9H 7)-Hf(NMe2)3 (4), which reacts reversibly with a second equivalent of 2 to form a binuclear complex, {μ-η5:η5-Me2Si(1-indenyl) 2}{Hf(NMe2)3}2 (5), and undergoes reversible intramolecular amine elimination to form rac-3 and meso-3. The novel C1-symmetric ansametallocene {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}Hf(NMe2)2 (6), in which one of the indenyl groups is bridged through the 2-position, is observed as a side product in the synthesis of 3. Complex 6 has been prepared in 21% isolated yield by thermolysis of 4 (or mixtures of 1 and 2) at 160 °C and can be converted to {Me2Si(η5-1-indenyl)(η 3-2-indenyl)}HfMe2 (7, 100% NMR) by reaction with AlMe3. The molecular structures of rac-3 and 6 have been determined by X-ray crystallography.

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U2 - 10.1021/om970242g

DO - 10.1021/om970242g

M3 - Article

AN - SCOPUS:0000130188

SN - 0276-7333

VL - 16

SP - 3044

EP - 3050

JO - Organometallics

JF - Organometallics

IS - 13

ER -

Synthesis and structures of rac-Me₂Si(η⁵-1-indenyl)₂Hf(NMe ₂)₂ and {Me₂Si(η⁵-1-indenyl)(η ³-2-indenyl)}Hf(NMe₂)₂

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