Preparation and characterization of monomeric and dimeric group IV metallocene dihydrides having alkyl- substituted cyclopentadienyl ligands

Paul J. Chirik

doi:10.1021/om9810293

Preparation and characterization of monomeric and dimeric group IV metallocene dihydrides having alkyl- substituted cyclopentadienyl ligands

Paul J. Chirik

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Abstract

A series of zirconocene dihydride complexes of the general form [(R_nCp)₂ZrH₂]_x having substituted cyclopentadienyl ligands has been prepared by hydrogenation of the corresponding dimethyl complexes. The most sterically crowded members (Cp*(η⁵-C₅HMe₄)ZrH₂, (Cp* = (η⁵-C₅Me₅)), Cp*{η⁵-C₅H₃-1,3-(CMe ₃)₂}ZrH₂ and {η⁵-C₅H₃-1,3-(CMe₃) ₂}₂ZrH₂) are monomeric; those less crowded members ([Cp*{η⁵-C₅H₄(CMe ₃)}ZrH₂]₂, [Cp*(THI)ZrH₂]₂ (THI = η⁵-tetrahydroindenyl), and [{η⁵-C₅H₃-1,3-(CHMe₂) ₂}₂ZrH₂]₂) are predominantly dimeric in benzene solution. Cp*{η⁵-C₅H₃-1,3-(CHMe ₂)₂}ZrH₂ and (η⁵-C₅HMe₄)₂ZrH₂ exist as equilibrium mixtures of monomer and dimer in benzene solution. The hydride ligands rapidly exchange with D₂, affording the dideuteride complexes. Deuterium incorporation into some of the substituents on the cyclopentadienyl rings of the monomeric dihydride complexes is also observed. The X-ray structures of Cp*₂HfH₂, Cp*{η⁵-C₅H₄(CMe ₃)}ZrCl₂, Cp*{η⁵-C₅H₃-1,3-(CHMe ₂)₂}ZrCl₂ and {η⁵-C₅H₃-1,3-(CMe₃) ₂}₂ZrCl₂ are reported.

Original language	English (US)
Pages (from-to)	1873-1881
Number of pages	9
Journal	Organometallics
Volume	18
Issue number	10
DOIs	https://doi.org/10.1021/om9810293
State	Published - May 10 1999
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om9810293

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@article{93d968d82be74838a049ce61681108bf,

title = "Preparation and characterization of monomeric and dimeric group IV metallocene dihydrides having alkyl- substituted cyclopentadienyl ligands",

abstract = "A series of zirconocene dihydride complexes of the general form [(RnCp)2ZrH2]x having substituted cyclopentadienyl ligands has been prepared by hydrogenation of the corresponding dimethyl complexes. The most sterically crowded members (Cp*(η5-C5HMe4)ZrH2, (Cp* = (η5-C5Me5)), Cp*{η5-C5H3-1,3-(CMe 3)2}ZrH2 and {η5-C5H3-1,3-(CMe3) 2}2ZrH2) are monomeric; those less crowded members ([Cp*{η5-C5H4(CMe 3)}ZrH2]2, [Cp*(THI)ZrH2]2 (THI = η5-tetrahydroindenyl), and [{η5-C5H3-1,3-(CHMe2) 2}2ZrH2]2) are predominantly dimeric in benzene solution. Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrH2 and (η5-C5HMe4)2ZrH2 exist as equilibrium mixtures of monomer and dimer in benzene solution. The hydride ligands rapidly exchange with D2, affording the dideuteride complexes. Deuterium incorporation into some of the substituents on the cyclopentadienyl rings of the monomeric dihydride complexes is also observed. The X-ray structures of Cp*2HfH2, Cp*{η5-C5H4(CMe 3)}ZrCl2, Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrCl2 and {η5-C5H3-1,3-(CMe3) 2}2ZrCl2 are reported.",

author = "Chirik, {Paul J.}",

year = "1999",

month = may,

day = "10",

doi = "10.1021/om9810293",

language = "English (US)",

volume = "18",

pages = "1873--1881",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "10",

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TY - JOUR

T1 - Preparation and characterization of monomeric and dimeric group IV metallocene dihydrides having alkyl- substituted cyclopentadienyl ligands

AU - Chirik, Paul J.

PY - 1999/5/10

Y1 - 1999/5/10

N2 - A series of zirconocene dihydride complexes of the general form [(RnCp)2ZrH2]x having substituted cyclopentadienyl ligands has been prepared by hydrogenation of the corresponding dimethyl complexes. The most sterically crowded members (Cp*(η5-C5HMe4)ZrH2, (Cp* = (η5-C5Me5)), Cp*{η5-C5H3-1,3-(CMe 3)2}ZrH2 and {η5-C5H3-1,3-(CMe3) 2}2ZrH2) are monomeric; those less crowded members ([Cp*{η5-C5H4(CMe 3)}ZrH2]2, [Cp*(THI)ZrH2]2 (THI = η5-tetrahydroindenyl), and [{η5-C5H3-1,3-(CHMe2) 2}2ZrH2]2) are predominantly dimeric in benzene solution. Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrH2 and (η5-C5HMe4)2ZrH2 exist as equilibrium mixtures of monomer and dimer in benzene solution. The hydride ligands rapidly exchange with D2, affording the dideuteride complexes. Deuterium incorporation into some of the substituents on the cyclopentadienyl rings of the monomeric dihydride complexes is also observed. The X-ray structures of Cp*2HfH2, Cp*{η5-C5H4(CMe 3)}ZrCl2, Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrCl2 and {η5-C5H3-1,3-(CMe3) 2}2ZrCl2 are reported.

AB - A series of zirconocene dihydride complexes of the general form [(RnCp)2ZrH2]x having substituted cyclopentadienyl ligands has been prepared by hydrogenation of the corresponding dimethyl complexes. The most sterically crowded members (Cp*(η5-C5HMe4)ZrH2, (Cp* = (η5-C5Me5)), Cp*{η5-C5H3-1,3-(CMe 3)2}ZrH2 and {η5-C5H3-1,3-(CMe3) 2}2ZrH2) are monomeric; those less crowded members ([Cp*{η5-C5H4(CMe 3)}ZrH2]2, [Cp*(THI)ZrH2]2 (THI = η5-tetrahydroindenyl), and [{η5-C5H3-1,3-(CHMe2) 2}2ZrH2]2) are predominantly dimeric in benzene solution. Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrH2 and (η5-C5HMe4)2ZrH2 exist as equilibrium mixtures of monomer and dimer in benzene solution. The hydride ligands rapidly exchange with D2, affording the dideuteride complexes. Deuterium incorporation into some of the substituents on the cyclopentadienyl rings of the monomeric dihydride complexes is also observed. The X-ray structures of Cp*2HfH2, Cp*{η5-C5H4(CMe 3)}ZrCl2, Cp*{η5-C5H3-1,3-(CHMe 2)2}ZrCl2 and {η5-C5H3-1,3-(CMe3) 2}2ZrCl2 are reported.

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U2 - 10.1021/om9810293

DO - 10.1021/om9810293

M3 - Article

AN - SCOPUS:0000441172

SN - 0276-7333

VL - 18

SP - 1873

EP - 1881

JO - Organometallics

JF - Organometallics

IS - 10

ER -

Preparation and characterization of monomeric and dimeric group IV metallocene dihydrides having alkyl- substituted cyclopentadienyl ligands

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