In:
Zeitschrift für Naturforschung B, Walter de Gruyter GmbH, Vol. 50, No. 12 ( 1995-12-1), p. 1818-1832
Abstract:
In the reaction of N-methylaminomethylene-dimethylphosphine oxide and sulfide with diethylaminotrimethylsilane, N-methyl-N-trimethylsilyl-aminomethylene-dimethylphosphine oxide (1) and sulfide (2) were formed. These compounds were allowed to react with a series of P(III)C1 compounds to give the corresponding methylaminomethylene-bridged diphosphorus compounds (3 - 10) with phosphorus in the combination λ 4 P(V)/λ 3 P(III). In the oxidation of some of these compounds by the hydrogen peroxide-urea 1:1-adduct (NH 2 ) 2 CO ·H 2 O 2 or sulfur, the corresponding λ 4 P-CH 2 -N(Me)-λ 4 P-derivatives (11 - 16) were formed. Different reaction behaviour was observed depending on the substituent at λ 4 P or on the oxidizing agent. Reaction of 1 with trimethylsilylmethyl tetrafiuorophosphorane and with bromotriphenylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphosphorus compounds (17 ) and (18) with phosphorus in the combination λ 4 P(V)/λ 5 P(V) (17) and λ 4 P(V)/λ 4 P(V) + (18). Oxidation of N-diphenylphosphino-N-methyl-aminomethylene-dimethylphosphine oxide (3) by tetrachloro-o-benzoquinone led to the corresponding addition product in impure form. Reaction of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated. Both oxidation ( 〉 N-PPh 2 → 〉 N-P(:O)Ph 2 ) and insertion of HFA into the P-N-bond ( 〉 N-PPh 2 → 〉 NC(CF 3 ) 2 -O-PPh 2 ) occurred. In the reaction of 1 with methyldichlorophosphine, both the mono- and disubstituted products, 22 and 23, were formed, independently of the reaction conditions and molar ratio of the starting compounds. The reaction of 1 with bis(diethylamino)chlorophosphine was unusual. Upon separation of both trimethylchlorosilane and dimethylaminotrimethylsilane, compounds 24 - 26 were formed, with the central phosphorus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively. Simultaneously, tris(diethylamino)phosphine was formed.
Type of Medium:
Online Resource
ISSN:
1865-7117
,
0932-0776
DOI:
10.1515/znb-1995-1208
Language:
English
Publisher:
Walter de Gruyter GmbH
Publication Date:
1995
detail.hit.zdb_id:
2078109-X
detail.hit.zdb_id:
124635-5
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