Synthesis and reactivity of titanium and zirconium complexes supported by a multidentate monoanionic [N 2 P 2] ligand

Wayne A. Chomitz; Andrew D. Sutton; Jamin L. Krinsky; John Arnold

doi:10.1021/om8011932

Synthesis and reactivity of titanium and zirconium complexes supported by a multidentate monoanionic [N ₂ P ₂] ligand

Wayne A. Chomitz, Andrew D. Sutton, Jamin L. Krinsky, John Arnold

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Abstract

The coordination chemistry of titanium and zirconium complexes supported by the monoanionic multidentate ligand [N ₂P ₂] (where [N ₂P ₂]) t BuN ^-SiMe ₂N(CH ₂CH ₂P ⁱPr ₂) ₂) is presented. The zirconium(IV) halide complex [N ₂P ₂] ZrCl ₃ (1) serves as a precursor to the alkyl species [N ₂P ₂]Zr(CH ₂SiMe ₃) ₃ (2) and [N ₂P ₂]ZrMe ₃ (3). The coordination behavior of the [N ₂P ₂] ligand in compound 3 is determined using NMR and X-ray diffraction data, and protonation of 3 results in the formation of the cationic species {[N ₂P ₂]ZrMe ₂}{B(C ₆H ₅) ₄}(4). The reduction of 1 in the presence of various traps leads to the isolation of ([N ₂P ₂]ZrCl) ₂(μ-η ²:η ²-N ₂)(5), ([N ₂P ₂]ZrCl) ₂(μ-Cl) ₂ (6), and [N ₂P ₂]ZrAr ^* (9). The titanium(III) halide complex [N ₂P ₂]TiCl ₂ (10) also serves as a precursor to alkyl and reduced species [N ₂P ₂]TiMe ₂ (11) and ([N ₂P ₂]TiCl) ₂(μ-N ₂)(12). Alkylation of 12 results in the formation of ([N ₂P ₂]TiCH ₂SiMe ₃) ₂(μ- N ₂)(13), and the degree of reduction of the N ₂ moiety in 12 and 13 is examined using X-ray crystallography and Raman spectroscopy. A series of titanium(IV) imido complexes [N ₂P ₂]TiCl(N ^tBu) (14), [N ₂P ₂]TiMe(N ^tBu) (15), and {[N ₂P ₂]Ti(N ^tBu)}{MeB(C ₆F ₅) ₃)} (16) are synthesized, and the coordination behavior of the [N ₂P ₂] ligand is presented.

Original language	English
Pages (from-to)	3338-3349
Number of pages	12
Journal	Organometallics
Volume	28
Issue number	12
DOIs	https://doi.org/10.1021/om8011932
State	Published - Jun 22 2009
Externally published	Yes

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@article{f0b7f3bda4e34235ab98bd9bdb2e7727,

title = "Synthesis and reactivity of titanium and zirconium complexes supported by a multidentate monoanionic [N 2 P 2] ligand",

abstract = "The coordination chemistry of titanium and zirconium complexes supported by the monoanionic multidentate ligand [N 2P 2] (where [N 2P 2]) t BuN -SiMe 2N(CH 2CH 2P iPr 2) 2) is presented. The zirconium(IV) halide complex [N 2P 2] ZrCl 3 (1) serves as a precursor to the alkyl species [N 2P 2]Zr(CH 2SiMe 3) 3 (2) and [N 2P 2]ZrMe 3 (3). The coordination behavior of the [N 2P 2] ligand in compound 3 is determined using NMR and X-ray diffraction data, and protonation of 3 results in the formation of the cationic species {[N 2P 2]ZrMe 2}{B(C 6H 5) 4}(4). The reduction of 1 in the presence of various traps leads to the isolation of ([N 2P 2]ZrCl) 2(μ-η 2:η 2-N 2)(5), ([N 2P 2]ZrCl) 2(μ-Cl) 2 (6), and [N 2P 2]ZrAr * (9). The titanium(III) halide complex [N 2P 2]TiCl 2 (10) also serves as a precursor to alkyl and reduced species [N 2P 2]TiMe 2 (11) and ([N 2P 2]TiCl) 2(μ-N 2)(12). Alkylation of 12 results in the formation of ([N 2P 2]TiCH 2SiMe 3) 2(μ- N 2)(13), and the degree of reduction of the N 2 moiety in 12 and 13 is examined using X-ray crystallography and Raman spectroscopy. A series of titanium(IV) imido complexes [N 2P 2]TiCl(N tBu) (14), [N 2P 2]TiMe(N tBu) (15), and {[N 2P 2]Ti(N tBu)}{MeB(C 6F 5) 3)} (16) are synthesized, and the coordination behavior of the [N 2P 2] ligand is presented.",

author = "Chomitz, {Wayne A.} and Sutton, {Andrew D.} and Krinsky, {Jamin L.} and John Arnold",

year = "2009",

month = jun,

day = "22",

doi = "10.1021/om8011932",

language = "English",

volume = "28",

pages = "3338--3349",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "12",

}

TY - JOUR

T1 - Synthesis and reactivity of titanium and zirconium complexes supported by a multidentate monoanionic [N 2 P 2] ligand

AU - Chomitz, Wayne A.

AU - Sutton, Andrew D.

AU - Krinsky, Jamin L.

AU - Arnold, John

PY - 2009/6/22

Y1 - 2009/6/22

N2 - The coordination chemistry of titanium and zirconium complexes supported by the monoanionic multidentate ligand [N 2P 2] (where [N 2P 2]) t BuN -SiMe 2N(CH 2CH 2P iPr 2) 2) is presented. The zirconium(IV) halide complex [N 2P 2] ZrCl 3 (1) serves as a precursor to the alkyl species [N 2P 2]Zr(CH 2SiMe 3) 3 (2) and [N 2P 2]ZrMe 3 (3). The coordination behavior of the [N 2P 2] ligand in compound 3 is determined using NMR and X-ray diffraction data, and protonation of 3 results in the formation of the cationic species {[N 2P 2]ZrMe 2}{B(C 6H 5) 4}(4). The reduction of 1 in the presence of various traps leads to the isolation of ([N 2P 2]ZrCl) 2(μ-η 2:η 2-N 2)(5), ([N 2P 2]ZrCl) 2(μ-Cl) 2 (6), and [N 2P 2]ZrAr * (9). The titanium(III) halide complex [N 2P 2]TiCl 2 (10) also serves as a precursor to alkyl and reduced species [N 2P 2]TiMe 2 (11) and ([N 2P 2]TiCl) 2(μ-N 2)(12). Alkylation of 12 results in the formation of ([N 2P 2]TiCH 2SiMe 3) 2(μ- N 2)(13), and the degree of reduction of the N 2 moiety in 12 and 13 is examined using X-ray crystallography and Raman spectroscopy. A series of titanium(IV) imido complexes [N 2P 2]TiCl(N tBu) (14), [N 2P 2]TiMe(N tBu) (15), and {[N 2P 2]Ti(N tBu)}{MeB(C 6F 5) 3)} (16) are synthesized, and the coordination behavior of the [N 2P 2] ligand is presented.

AB - The coordination chemistry of titanium and zirconium complexes supported by the monoanionic multidentate ligand [N 2P 2] (where [N 2P 2]) t BuN -SiMe 2N(CH 2CH 2P iPr 2) 2) is presented. The zirconium(IV) halide complex [N 2P 2] ZrCl 3 (1) serves as a precursor to the alkyl species [N 2P 2]Zr(CH 2SiMe 3) 3 (2) and [N 2P 2]ZrMe 3 (3). The coordination behavior of the [N 2P 2] ligand in compound 3 is determined using NMR and X-ray diffraction data, and protonation of 3 results in the formation of the cationic species {[N 2P 2]ZrMe 2}{B(C 6H 5) 4}(4). The reduction of 1 in the presence of various traps leads to the isolation of ([N 2P 2]ZrCl) 2(μ-η 2:η 2-N 2)(5), ([N 2P 2]ZrCl) 2(μ-Cl) 2 (6), and [N 2P 2]ZrAr * (9). The titanium(III) halide complex [N 2P 2]TiCl 2 (10) also serves as a precursor to alkyl and reduced species [N 2P 2]TiMe 2 (11) and ([N 2P 2]TiCl) 2(μ-N 2)(12). Alkylation of 12 results in the formation of ([N 2P 2]TiCH 2SiMe 3) 2(μ- N 2)(13), and the degree of reduction of the N 2 moiety in 12 and 13 is examined using X-ray crystallography and Raman spectroscopy. A series of titanium(IV) imido complexes [N 2P 2]TiCl(N tBu) (14), [N 2P 2]TiMe(N tBu) (15), and {[N 2P 2]Ti(N tBu)}{MeB(C 6F 5) 3)} (16) are synthesized, and the coordination behavior of the [N 2P 2] ligand is presented.

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U2 - 10.1021/om8011932

DO - 10.1021/om8011932

M3 - Article

AN - SCOPUS:67449111008

SN - 0276-7333

VL - 28

SP - 3338

EP - 3349

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Synthesis and reactivity of titanium and zirconium complexes supported by a multidentate monoanionic [N ₂ P ₂] ligand

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