Water-Soluble Phosphines. 6.1 Tailor-Made Syntheses of Chiral Secondary and Tertiary Phosphines with Sulfonated Aromatic Substituents: Structural and Quantum Chemical Studies
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- 作者：Frank Bitterer ; Oliver Herd ; Antonella Hessler ; Michael Kü ; hnel ; Karsten Rettig ; Othmar Stelzer ; William S. Sheldrick ; Sabine Nagel ; and Notker Rö ; sch
- 刊名：Inorganic Chemistry
- 出版年：1996
- 出版时间：July 3, 1996
- 年：1996
- 卷：35
- 期：14
- 页码：4103 - 4113
- 全文大小：410K
- 年卷期：v.35,no.14(July 3, 1996)
- ISSN：1520-510X
文摘
Chiral water-soluble secondary phosphines(2-6) were obtained by nucleophilicphosphination ofFC6H4-4-SO3K(1a),FC6H3-2,4-(SO3K)2(1b), and FC6H4-2-SO3K(1c) with RPH2 (R = Ph,2,4,6-Me3C6H2,2,4,6-iPr3C6H2) inthe superbasic medium DMSO/KOH by employing steric control ofsubstitution at phosphorus by bulky substituentsR and sulfonic groups in the ortho position of the aromatic ringsystems in 1b or 1c. The secondaryphosphinesmay be deprotonated in DMSO/KOH to give phosphido anions which onreaction with alkyl halides (PhCH2Cl,Br(CH2)3Br, andC12H25Br) yield mono- or bidentatetertiary phosphines (7-10).Ligands of this type arealternatively accessible by nucleophilic arylation of secondaryphosphines, e.g. Ph(Me)PH orPh(H)P(CH2)3P(H)Ph with 1a or 1b, respectively. Thecrystal structure of the starting material1b·H2O (space groupP21/m) hasbeen determined. In the solid state of1b·H2O the individual molecules areinterconnected by ionic interactionsbetween the potassium cations and the SO3-anions. The C-F bond (C(1)-F 1.347(4) Å) is shorter thanthat inC6H5F (1.356(4) Å). The unit cell of7a·0.5H2O (space group P
),the first structurally characterized chiralphosphine with a sulfonated phenyl substituent, contains the twoenantiomers. Due to the asymmetrical substitutionat phosphorus the PC3 skeletons are significantly distorted(P(1)-C(1,11,31) 1.864(10), 1.825(8),1.841(7) Å).The electronic structure of sulfonated fluorobenzenesFC6H5-n(SO3M)n(M = K, NH4, n = 1-3) is discussedonthe basis of quantum chemical calculations. In particular, thereactivity difference toward nucleophilic phosphinationwithin the series is rationalized in terms of steric factors and of the-I effect of the sulfonic groups.
),the first structurally characterized chiralphosphine with a sulfonated phenyl substituent, contains the twoenantiomers. Due to the asymmetrical substitutionat phosphorus the PC3 skeletons are significantly distorted(P(1)-C(1,11,31) 1.864(10), 1.825(8),1.841(7) Å).The electronic structure of sulfonated fluorobenzenesFC6H5-n(SO3M)n(M = K, NH4, n = 1-3) is discussedonthe basis of quantum chemical calculations. In particular, thereactivity difference toward nucleophilic phosphinationwithin the series is rationalized in terms of steric factors and of the-I effect of the sulfonic groups.