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Iminophosphines: Synthesis, formation of 2,3-dihydro-1 H-benzo[1,3]azaphosphol-3-ium salts and N-(pyridin-2-yl)-2-diphenylphosphinoylaniline, coordination chemistry and applications in platinum group catalyzed Suzuki coupling reactions and hydrosilylations

Lookup NU author(s): Dr Simon DohertyORCiD, Dr Julian Knight, Thomas Scanlan, Dr Mark Elsegood, Emeritus Professor Bill CleggORCiD


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The aprotic and protic bi- and multidentate iminophosphines 2-Ph2PC6H4N=CR1R2 (R1 = H, R2 = Ph = 2a; R1 = Me R2 = Ph = 2b; R1 = H, R2 = 2-thienyl = 2c; R1 = H, R2 = C6H4-2-PPh2 = 2d; R1 = H, R2 = C6H4-2-OH = 2e, R1 + H,R2 = C6H4-2-OH-3Bu′ = 2f: R1 = H, R2 = CH2C(O)Me = 2g) have been prepared by the acid catalyzed condensation of 2-(diphenylphosphino)aniline with the corresponding aldehyde-ketone. Iminophosphine 2d can be reduced with sodium cyanoborohydride to give the corresponding amino-diphosphine has been characterized by single-crystal X-ray crystallography, as its palladium dichloride derivative. The attempted condensation of 2-(diphenylphosphino)aniline with pyridine-2-carboxaldehyde to give the corresponding pyridine-functionalized iminophosphine resulted in an unusual transformation involving the diastereoselective addition of two equivalents of aldehyde to give 1,2-dipyridin-2-yl-2-(o-diphenylphosphinoyl) phenylamino-ethanol, which has been characterized by a single-crystal X-ray structure determination. The bidentate iminosphosphine 2-Ph2PC6H4N=C(H)Ph reacts with [(cycloocta-1,5-diene)PdCIX] X = Cl. Me) to give [Pd 2- Ph2PC6H4N-C(H)Ph|CIX] and the imino-diphosphine 2-Ph2PC6H4N=C(H)C6H4-PPh2 reacts with [(cycloocta-1,5-diene)PdClMe] to give [Pd|2-Ph2PC6H4N=C(H)C6H4-PPh2}ClMe] and each has been characterized by single-crystal X-ray crystallography. The monobasic iminophosphine 2-Ph2PC6H4N=C(Me)CH2C(O)Me reacts with [Ni(PPh3)2Cl2] in the presence of NaH to give the phosphino-ketoiminate complex [Ni{2-Ph2PC6H4N=C(Me)CHC(O)Me}Cl], which has been structurally characterized. Mixtures of iminophosphines 2a-h and a palladium source catalyze the Suzuki cross coupling of 4-bromoacetophenone with phenyl boronic acid. The efficiency of these catalysts show a marked dependence on the palladium source, catalysts formed from [Pd2(OAc)6 giving consistently higher conversions than those formed from [Pd2(dba)3] and [PdCl2(MeCN)2]. Catalysts formed from neutral bi- and terdentate iminophosphines 2a-d gave significantly higher conversions than those formed from their monobasic counterparts 2e-f. Notably, under our conditions the conversions obtained with 2a-c compare favorably with those palladium. In addition, mixtures of [Ir(COD)Cl]2 and 2a-h are active for the hydrosilytation of acetophenone; in this case catalysts formed from monobasic iminophosphines 2e-f giving the highest conversions. © 2002 Elsevier Science B.V. All rights reserved.

Publication metadata

Author(s): Doherty S, Knight JG, Scanlan TH, Elsegood MRJ, Clegg W

Publication type: Review

Publication status: Published

Journal: Journal of Organometallic Chemistry

Year: 2002

Volume: 650

Issue: 1-2

Pages: 231-248

ISSN (print): 0022-328X

ISSN (electronic): 1872-8561


DOI: 10.1016/S0022-328X(02)01203-2