1996
DOI: 10.1002/zaac.19966220724
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Synthesis and Characterization of 2‐Arylseleno‐2‐chloro‐1,2,3‐triorgano‐1,3,2λ5‐diazaphosphetidin‐4‐ones

Abstract: The reactions of N,N′‐dimethyl‐N,N′‐bis(trimethylsilyl)urea 8 and N‐methyl‐N′‐phenyl‐N,N′‐bis(trimethylsilyl)urea 9 with phenylselenenyl chloride 6 and p‐chlorophenylselenenyl chloride 7 furnished the N‐arylseleno‐N,N′‐diorgano‐N′‐(trimethylsilyl)ureas 10–13. The reactions of 10–13 with MePCl2 and PhPCl2 resulted in the formation of a new class of compounds, the 2‐arylseleno‐2‐chloro‐1,2,3‐triorgano‐1,3,2λ5‐diazaphosphetidin‐4‐ones 14–19. The new selenophosphoranes 20 and 21 were obtained in the reaction of 15… Show more

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Cited by 6 publications
(2 citation statements)
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“…The Se-I bond in 2, 3.2972(8) A ˚, is slightly longer than observed for Ph 3 PSe(Ph)I, 3.2564(5) A ˚, reflecting the increased basicity of (m-CH 3 C 6 H 4 ) 3 P compared with Ph 3 P. The P-Se bond in 2 is 2.2612(8) A ˚, and is similar in magnitude to both Ph 3 PSe(Ph)I, [P-Se: 2.2585(9) A ˚], 12 and other reported data for P-Se single bonds, such as in P 4 Se 3 (average P-Se: 2.24(1) A ˚), 19 and a number of 5-coordinate arylseleno-phosphoranes, where the P-Se bonds vary between 2.233(2) and 2.2432(13) A ˚. 20 The lengthening of the Se-I bond in 2 compared to Ph 3 PSe(Ph)I is contrary to expectations as the introduction of a more basic phosphine would be expected to weaken the Se-I bond, and strengthen the P-Se bond. This suggests that steric factors are important in 2, with the crystallographic cone angle of the (m-CH 3 C 6 H 4 ) 3 P group in 2 calculated to be 165 • , significantly larger than the cone angle of Ph 3 P in Ph 3 PSe(Ph)I, calculated as 149 • .…”
Section: Resultsmentioning
confidence: 87%
“…The Se-I bond in 2, 3.2972(8) A ˚, is slightly longer than observed for Ph 3 PSe(Ph)I, 3.2564(5) A ˚, reflecting the increased basicity of (m-CH 3 C 6 H 4 ) 3 P compared with Ph 3 P. The P-Se bond in 2 is 2.2612(8) A ˚, and is similar in magnitude to both Ph 3 PSe(Ph)I, [P-Se: 2.2585(9) A ˚], 12 and other reported data for P-Se single bonds, such as in P 4 Se 3 (average P-Se: 2.24(1) A ˚), 19 and a number of 5-coordinate arylseleno-phosphoranes, where the P-Se bonds vary between 2.233(2) and 2.2432(13) A ˚. 20 The lengthening of the Se-I bond in 2 compared to Ph 3 PSe(Ph)I is contrary to expectations as the introduction of a more basic phosphine would be expected to weaken the Se-I bond, and strengthen the P-Se bond. This suggests that steric factors are important in 2, with the crystallographic cone angle of the (m-CH 3 C 6 H 4 ) 3 P group in 2 calculated to be 165 • , significantly larger than the cone angle of Ph 3 P in Ph 3 PSe(Ph)I, calculated as 149 • .…”
Section: Resultsmentioning
confidence: 87%
“…The two independent cations differ insignificantly, so only one will be discussed. The phosphorus atom, as expected, displays somewhat distorted tetrahedral coordination geometry, with the largest deviations from ideal angles for N1±P1±C11 [103.07 (13) The selenium-phosphorus bond [230.27(9) pm] is much longer than that of the selenophosphonium cations in (triphenylmethylseleno)phosphonium perchlorate [13] 220.5 pm and tricarbonyl(cyclopentadienyl)(selenotriphenylphosphonium) tungsten(I) perchlorate [14] 219.44 (14) pm, and also longer than those of the selenophosphoranes 2-chloro-1,2dimethyl-3-phenyl-2-phenylseleno-1,3,2d 5 -diaza-phosphetidin-4-one 5 [223.9(2) pm], and 1,3-dimethyl-2-(4chlorophenylseleno)-2-(4-nitrophenoxy)-2-phenyl-1,3,2d 5 -diazaphosphetidin-4-one 6 [224.32(13) pm] [15]. The weakening of the P±Se bond in 4 a may be a compensating effect for the strong P±N bonds; more Cl1 is connected to three, Cl2 to four water molecules (see Figure 2).…”
Section: Resultsmentioning
confidence: 99%