Novel η3-allyl complexes of titanium

Albert F. Cotton; Carlos A. Murillo; Marina A. Petrukhina

doi:10.1016/S0022-328X(99)00192-8

Novel η³-allyl complexes of titanium

Albert F. Cotton
, Carlos A. Murillo
, Marina A. Petrukhina

Chemistry

University at Albany

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

22 Scopus citations

Abstract

Treatment of TiCl₄(dmpe) (1a) and TiCl₄(depe) (1b) with two equivalents of C₃H₅MgCl in toluene at -30°C affords two novel allyl-titanium complexes: a dinuclear mixed-valent Ti₂⁵⁺ species Ti₂(μ-Cl)₂Cl₂(dmpe)₂(μ²-η³-C₃H₅) (2) and a mononuclear Ti^III complex, TiCl(depe)(η³-C₃H₅)₂ (3). Syntheses and crystal structures of 1b, 2 and 3 are presented. In complex 2, in addition to two bridging chloride ligands a η³-allyl group spans two titanium atoms with a Ti...Ti separation of 2.908(1) Å. The allyl bridge is symmetrical with each terminal carbon atom having a Ti-C distance of 2.154(6) Å, while the central carbon atom is equidistant from the titanium atoms, Ti-C_cent, 2.430(6) Å. Each Ti atom in 2 is further coordinated by a chelating dmpe ligand and a chloride ion. In the mononuclear complex 3 two η³-allyl groups are bound to the Ti^III center and the coordination is completed by a chelating diphosphine ligand and one chloride ion. The Ti-C distances in 3 vary from 2.286(3) to 2.478(3) Å.

Original language	English
Pages (from-to)	1-6
Number of pages	6
Journal	Journal of Organometallic Chemistry
Volume	593-594
DOIs	https://doi.org/10.1016/S0022-328X(99)00192-8
State	Published - Jan 15 2000

Keywords

Allyl ligands
Crystal structures
Titanium complexes

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10.1016/S0022-328X(99)00192-8

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@article{a7bd2a6014aa49fd9ad1af18e107db8b,

title = "Novel η3-allyl complexes of titanium",

abstract = "Treatment of TiCl4(dmpe) (1a) and TiCl4(depe) (1b) with two equivalents of C3H5MgCl in toluene at -30°C affords two novel allyl-titanium complexes: a dinuclear mixed-valent Ti25+ species Ti2(μ-Cl)2Cl2(dmpe)2(μ2-η3-C3H5) (2) and a mononuclear TiIII complex, TiCl(depe)(η3-C3H5)2 (3). Syntheses and crystal structures of 1b, 2 and 3 are presented. In complex 2, in addition to two bridging chloride ligands a η3-allyl group spans two titanium atoms with a Ti...Ti separation of 2.908(1) {\AA}. The allyl bridge is symmetrical with each terminal carbon atom having a Ti-C distance of 2.154(6) {\AA}, while the central carbon atom is equidistant from the titanium atoms, Ti-Ccent, 2.430(6) {\AA}. Each Ti atom in 2 is further coordinated by a chelating dmpe ligand and a chloride ion. In the mononuclear complex 3 two η3-allyl groups are bound to the TiIII center and the coordination is completed by a chelating diphosphine ligand and one chloride ion. The Ti-C distances in 3 vary from 2.286(3) to 2.478(3) {\AA}.",

keywords = "Allyl ligands, Crystal structures, Titanium complexes",

author = "Cotton, \{Albert F.\} and Murillo, \{Carlos A.\} and Petrukhina, \{Marina A.\}",

year = "2000",

month = jan,

day = "15",

doi = "10.1016/S0022-328X(99)00192-8",

language = "English",

volume = "593-594",

pages = "1--6",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Novel η3-allyl complexes of titanium

AU - Cotton, Albert F.

AU - Murillo, Carlos A.

AU - Petrukhina, Marina A.

PY - 2000/1/15

Y1 - 2000/1/15

N2 - Treatment of TiCl4(dmpe) (1a) and TiCl4(depe) (1b) with two equivalents of C3H5MgCl in toluene at -30°C affords two novel allyl-titanium complexes: a dinuclear mixed-valent Ti25+ species Ti2(μ-Cl)2Cl2(dmpe)2(μ2-η3-C3H5) (2) and a mononuclear TiIII complex, TiCl(depe)(η3-C3H5)2 (3). Syntheses and crystal structures of 1b, 2 and 3 are presented. In complex 2, in addition to two bridging chloride ligands a η3-allyl group spans two titanium atoms with a Ti...Ti separation of 2.908(1) Å. The allyl bridge is symmetrical with each terminal carbon atom having a Ti-C distance of 2.154(6) Å, while the central carbon atom is equidistant from the titanium atoms, Ti-Ccent, 2.430(6) Å. Each Ti atom in 2 is further coordinated by a chelating dmpe ligand and a chloride ion. In the mononuclear complex 3 two η3-allyl groups are bound to the TiIII center and the coordination is completed by a chelating diphosphine ligand and one chloride ion. The Ti-C distances in 3 vary from 2.286(3) to 2.478(3) Å.

AB - Treatment of TiCl4(dmpe) (1a) and TiCl4(depe) (1b) with two equivalents of C3H5MgCl in toluene at -30°C affords two novel allyl-titanium complexes: a dinuclear mixed-valent Ti25+ species Ti2(μ-Cl)2Cl2(dmpe)2(μ2-η3-C3H5) (2) and a mononuclear TiIII complex, TiCl(depe)(η3-C3H5)2 (3). Syntheses and crystal structures of 1b, 2 and 3 are presented. In complex 2, in addition to two bridging chloride ligands a η3-allyl group spans two titanium atoms with a Ti...Ti separation of 2.908(1) Å. The allyl bridge is symmetrical with each terminal carbon atom having a Ti-C distance of 2.154(6) Å, while the central carbon atom is equidistant from the titanium atoms, Ti-Ccent, 2.430(6) Å. Each Ti atom in 2 is further coordinated by a chelating dmpe ligand and a chloride ion. In the mononuclear complex 3 two η3-allyl groups are bound to the TiIII center and the coordination is completed by a chelating diphosphine ligand and one chloride ion. The Ti-C distances in 3 vary from 2.286(3) to 2.478(3) Å.

KW - Allyl ligands

KW - Crystal structures

KW - Titanium complexes

UR - https://www.scopus.com/pages/publications/0034650001

U2 - 10.1016/S0022-328X(99)00192-8

DO - 10.1016/S0022-328X(99)00192-8

M3 - Article

SN - 0022-328X

VL - 593-594

SP - 1

EP - 6

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

ER -

Novel η³-allyl complexes of titanium

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