Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP((NHBu)-Bu-t)(3)

Stuart D. Robertson, Tristram Chivers, Jari Konu

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

Reactions of ((BuHN)-Bu-t)(3)PNSiMe3 (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes [MeZn{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}] (2), [Me2Al((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)2}] (3) and [Mg{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}(2)] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 center dot 2THF) or one molecule of TMEDA (5 center dot TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me2Al[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)]MgBu} Li center dot 4THF (6 center dot 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al-Me group to give {MeIAI[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)Mg]} (7). Complexes 5 center dot 2THF, 5 center dot TMEDA, 6 center dot 4THF and 7 have been characterized in solution by multinuclear (H-1, C-13, P-31 and Li-7) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 center dot 2THF have been determined by X-ray crystallography. (c) 2007 Elsevier B.V. All rights reserved.

LanguageEnglish
Pages4327-4336
Number of pages10
JournalJournal of Organometallic Chemistry
Volume692
Issue number20
DOIs
Publication statusPublished - 15 Sep 2007

Fingerprint

Aluminum
Magnesium
magnesium
Zinc
phosphates
Phosphates
zinc
Derivatives
aluminum
Molecules
X ray crystallography
Metals
Iodine
Nuclear magnetic resonance spectroscopy
Protons
Lithium
X Ray Crystallography
Magnetic Resonance Spectroscopy
phenyllithium
metals

Keywords

  • aluminum
  • magnesium
  • zinc
  • imidophosphates
  • structures
  • x-ray diffraction
  • phosphorous-containing radicals
  • complexes
  • ligands
  • anions

Cite this

@article{0e4d7888ab45488ab72ee2c407e1a4ff,
title = "Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP((NHBu)-Bu-t)(3)",
abstract = "Reactions of ((BuHN)-Bu-t)(3)PNSiMe3 (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes [MeZn{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}] (2), [Me2Al((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)2}] (3) and [Mg{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}(2)] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 center dot 2THF) or one molecule of TMEDA (5 center dot TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me2Al[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)]MgBu} Li center dot 4THF (6 center dot 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al-Me group to give {MeIAI[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)Mg]} (7). Complexes 5 center dot 2THF, 5 center dot TMEDA, 6 center dot 4THF and 7 have been characterized in solution by multinuclear (H-1, C-13, P-31 and Li-7) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 center dot 2THF have been determined by X-ray crystallography. (c) 2007 Elsevier B.V. All rights reserved.",
keywords = "aluminum, magnesium, zinc, imidophosphates, structures, x-ray diffraction, phosphorous-containing radicals, complexes, ligands, anions",
author = "Robertson, {Stuart D.} and Tristram Chivers and Jari Konu",
year = "2007",
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Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP((NHBu)-Bu-t)(3). / Robertson, Stuart D.; Chivers, Tristram; Konu, Jari.

In: Journal of Organometallic Chemistry, Vol. 692, No. 20, 15.09.2007, p. 4327-4336.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Organo-aluminum, zinc and magnesium derivatives of the imidotris(amido)phosphate Me3SiNP((NHBu)-Bu-t)(3)

AU - Robertson, Stuart D.

AU - Chivers, Tristram

AU - Konu, Jari

PY - 2007/9/15

Y1 - 2007/9/15

N2 - Reactions of ((BuHN)-Bu-t)(3)PNSiMe3 (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes [MeZn{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}] (2), [Me2Al((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)2}] (3) and [Mg{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}(2)] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 center dot 2THF) or one molecule of TMEDA (5 center dot TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me2Al[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)]MgBu} Li center dot 4THF (6 center dot 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al-Me group to give {MeIAI[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)Mg]} (7). Complexes 5 center dot 2THF, 5 center dot TMEDA, 6 center dot 4THF and 7 have been characterized in solution by multinuclear (H-1, C-13, P-31 and Li-7) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 center dot 2THF have been determined by X-ray crystallography. (c) 2007 Elsevier B.V. All rights reserved.

AB - Reactions of ((BuHN)-Bu-t)(3)PNSiMe3 (1) with the alkyl-metal reagents dimethylzinc, trimethylaluminum and di-n-butylmagnesium yield the monodeprotonated complexes [MeZn{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}] (2), [Me2Al((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)2}] (3) and [Mg{((NBu)-Bu-t)(NSiMe3)P((NHBu)-Bu-t)(2)}(2)] (4), respectively. Attempts to further deprotonate complex 2 with n-butyllithium or di-n-butylmagnesium result in nucleophilic displacement of the methylzinc fragment by lithium or magnesium. The two remaining amino protons of 3 are removed by reaction with di-n-butylmagnesium to give a heterobimetallic complex in which the coordination sphere of magnesium is completed by two molecules of THF (5 center dot 2THF) or one molecule of TMEDA (5 center dot TMEDA). Reaction of complex 3 with 1 equiv. of n-butyllithium followed by treatment of the product with di-n-butylmagnesium yields the complex {Me2Al[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)]MgBu} Li center dot 4THF (6 center dot 4THF), the first example of a triply deprotonated complex of 1 containing three different metals. Reaction of complex 5 with iodine results in cleavage of an Al-Me group to give {MeIAI[((NBu)-Bu-t)(NSiMe3)P((NBu)-Bu-t)(2)Mg]} (7). Complexes 5 center dot 2THF, 5 center dot TMEDA, 6 center dot 4THF and 7 have been characterized in solution by multinuclear (H-1, C-13, P-31 and Li-7) NMR spectroscopy, while the solid-state structures of 2, 4 and 5 center dot 2THF have been determined by X-ray crystallography. (c) 2007 Elsevier B.V. All rights reserved.

KW - aluminum

KW - magnesium

KW - zinc

KW - imidophosphates

KW - structures

KW - x-ray diffraction

KW - phosphorous-containing radicals

KW - complexes

KW - ligands

KW - anions

U2 - 10.1016/j.jorganchem.2007.06.064

DO - 10.1016/j.jorganchem.2007.06.064

M3 - Article

VL - 692

SP - 4327

EP - 4336

JO - Journal of Organometallic Chemistry

T2 - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 20

ER -