Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

J. Niemeyer; M. J. Kelly; I. M. Riddlestone; D. Vidovic; S. Aldridge

doi:10.1039/c5dt00131e

Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

J. Niemeyer, M. J. Kelly, I. M. Riddlestone, D. Vidovic, S. Aldridge

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

14 Citations (Scopus)

Abstract

The synthetic and reaction chemistries of cationic iminoborylene complexes [L_nM=B=N=CR₂]⁺, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)₂B(Cl)NCAr₂ (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)₂BCl₂ and suitable lithiated ketimines - a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy₃ or PPh₃), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR₃)(CO)(BNCAr₂)]⁺[BAr^X ₄]^- (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; Ar^X = 3,5-X₂C₆H₃ where X = Cl, CF₃) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M=B metathesis reactivity with a carbodiimide, and results in Fe=B cleavage and formation of the isonitrile complexes [CpFe(PCy₃)(CO)(CNR)]⁺[BAr^Cl ₄]^- (R = ⁱPr/Cy, 16/17).

Original language	English
Pages (from-to)	11294-11305
Number of pages	12
Journal	Dalton Transactions
Volume	44
Issue number	25
DOIs	https://doi.org/10.1039/c5dt00131e
Publication status	Published - 7 Jul 2015
Externally published	Yes

Access to Document

10.1039/c5dt00131e

Cite this

@article{b9b5e622f5c2489faa86729b9e70b862,

title = "Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides",

abstract = "The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM=B=N=CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines - a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX 4]- (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M=B metathesis reactivity with a carbodiimide, and results in Fe=B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl 4]- (R = iPr/Cy, 16/17).",

author = "J. Niemeyer and Kelly, {M. J.} and Riddlestone, {I. M.} and D. Vidovic and S. Aldridge",

year = "2015",

month = jul,

day = "7",

doi = "10.1039/c5dt00131e",

language = "English",

volume = "44",

pages = "11294--11305",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "The Royal Society of Chemistry",

number = "25",

}

TY - JOUR

T1 - Iminoborylene complexes

T2 - evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

AU - Niemeyer, J.

AU - Kelly, M. J.

AU - Riddlestone, I. M.

AU - Vidovic, D.

AU - Aldridge, S.

PY - 2015/7/7

Y1 - 2015/7/7

N2 - The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM=B=N=CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines - a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX 4]- (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M=B metathesis reactivity with a carbodiimide, and results in Fe=B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl 4]- (R = iPr/Cy, 16/17).

AB - The synthetic and reaction chemistries of cationic iminoborylene complexes [LnM=B=N=CR2]+, which feature a unique heterocumulene structure, have been systematically investigated. Precursors of the type CpFe(CO)2B(Cl)NCAr2 (Ar = p-Tol/Mes, 5c/d) have been generated by B-centred substitution chemistry using CpFe(CO)2BCl2 and suitable lithiated ketimines - a reaction which is found to be highly sensitive to the steric bulk at both the metal fragment and the ketimino group. Carbonyl/phosphine exchange (using PCy3 or PPh3), followed by halide abstraction allows for the generation of the cationic iminoborylenes [CpFe(PR3)(CO)(BNCAr2)]+[BArX 4]- (R = Cy, Ar = p-Tol/Mes, 12c/d; R = Ph, Ar = Mes, 13d; ArX = 3,5-X2C6H3 where X = Cl, CF3) which have been characterized spectroscopically and by X-ray crystallography. The reactivity of these iminoborylene systems towards a range of nucleophiles and unsaturated substrates has been investigated. The latter includes the first examples of M=B metathesis reactivity with a carbodiimide, and results in Fe=B cleavage and formation of the isonitrile complexes [CpFe(PCy3)(CO)(CNR)]+[BArCl 4]- (R = iPr/Cy, 16/17).

UR - http://www.scopus.com/inward/record.url?scp=84935000841&partnerID=8YFLogxK

U2 - 10.1039/c5dt00131e

DO - 10.1039/c5dt00131e

M3 - Article

AN - SCOPUS:84935000841

SN - 1477-9226

VL - 44

SP - 11294

EP - 11305

JO - Dalton Transactions

JF - Dalton Transactions

IS - 25

ER -

Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides

Abstract

Access to Document

Other files and links

Erratum: Iminoborylene complexes: evaluation of synthetic routes towards BN-allenylidenes and unexpected reactivity towards carbodiimides (Dalton Trans. (2015) 10.1039/c5dt00131e)

Cite this