J 1995

Strongly basic proazaphosphatranes: P(EtNCH2CH2)(3)N and P(iso-PrNCH2CH2)(3)N

WROBLEWSKI, A. E., Jiří PINKAS and J. G. VERKADE

Basic information

Original name

Strongly basic proazaphosphatranes: P(EtNCH2CH2)(3)N and P(iso-PrNCH2CH2)(3)N

Authors

WROBLEWSKI, A. E., Jiří PINKAS and J. G. VERKADE

Edition

Main Group Chemistry, READING, UK, GORDON BREACH SCI PUBL LTD, 1995, 1024-1221

Other information

Language

English

Type of outcome

Článek v odborném periodiku

Field of Study

10402 Inorganic and nuclear chemistry

Country of publisher

United States of America

Confidentiality degree

není předmětem státního či obchodního tajemství

Organization unit

Faculty of Science

Keywords in English

PRO-AZAPHOSPHATRANES; BOND; ATRANES; SYSTEMS; CRYSTAL; ATOMS

Tags

Změněno: 15/8/2001 12:00, prof. RNDr. Jiří Pinkas, Ph.D.

Abstract

V originále

The two new azaphosphatranes HP(RNCH2CH2)(3)N+Cl- (R = Et, 2c and R = i-Pr, 2d) were prepared from the corresponding (RNHCH2CH2)(3)N and CIP(NEt2)(2). They were transformed into the title proazaphosphatranes 3c and 3d, respectively, with tert-BuOK. Alternatively, 3d was prepared by the transamination reaction of PCl(NMe2)(2) with (iso-PrNCH2CH2)(3)N followed by deprotonation with tert-BuOK. Azaphosphatrane cation salts of 3d, [Z-P(iso-PrNCH2CH2)(3)N](+) (Z = H, 2d; X = D, 2d-D) were obtained from the reaction of 3d with ZCl. Competitive deprotonations of azaphosphatrane cation pairs with a stoichiometric deficit of tert-BuOK in DMSO showed the order of basicity: 3c > 3d > P(MeNCH2CH2)(3)N (3b). Compound 3d is also a more efficient catalyst for the trimerization of phenyl isocyanate to phenylisocyanurate than is 3b. A strong correlation (r = 0.996) of the transannular distance with the distance of the P from the plane of its amido nitrogens in nine compounds of the type [ZP(RNCH2CH2)(3)N](+) is observed. The molecular structure of 3d shows a P-N-ax distance of 3.29 Angstrom, which is 1.8% shorter than the sum of the corresponding van der Waals radii. Crystal data for 3d: a = 9.380 (2) Angstrom, b = 11.979(2) Angstrom, c = 16.063(3) Angstrom, beta = 95.62(1)degrees, V = 1796.2(6) Angstrom(3), Z = 4, space group P2(1)/n, R(F-o(2)) = 3.62%. The molecular structure of 2d exhibits a transannular R-N-ax bond of 1.95 Angstrom in a nearly undistorted trigonal bipyramidal phosphorus. Crystal data for 2d: a = 9.143(4) Angstrom, b = 9.319(4) Angstrom, c = 11.616(3) Angstrom, alpha = 87.07(3)degrees, beta = 88.64(3)degrees, gamma = 80.62(3)degrees, V = 972.8(6) Angstrom(3), Z = 2, space group P (1) over bar, R = 3.42%.