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

J 1995

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

WROBLEWSKI, A. E.; Jiří PINKAS a J. G. VERKADE

Základní údaje

Originální název

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

Autoři

WROBLEWSKI, A. E.; Jiří PINKAS a J. G. VERKADE

Vydání

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

Další údaje

Jazyk

angličtina

Typ výsledku

Článek v odborném periodiku

Obor

10402 Inorganic and nuclear chemistry

Stát vydavatele

Spojené státy

Utajení

není předmětem státního či obchodního tajemství

Označené pro přenos do RIV

Ano

Organizační jednotka

Přírodovědecká fakulta

Klíčová slova anglicky

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

Štítky

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

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

Anotace

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%.

Citovat

WROBLEWSKI, A. E.; Jiří PINKAS a J. G. VERKADE. Strongly basic proazaphosphatranes: P(EtNCH2CH2)(3)N and P(iso-PrNCH2CH2)(3)N. Main Group Chemistry. READING, UK: GORDON BREACH SCI PUBL LTD, 1995, roč. 1, č. 1, s. 69-79. ISSN 1024-1221.

@article{366819,
   author = {Wroblewski, A. E. and Pinkas, Jiří and Verkade, J. G.},
   article_location = {READING, UK},
   article_number = {1},
   keywords = {PRO-AZAPHOSPHATRANES; BOND; ATRANES; SYSTEMS; CRYSTAL; ATOMS},
   language = {eng},
   issn = {1024-1221},
   journal = {Main Group Chemistry},
   title = {Strongly basic proazaphosphatranes: P(EtNCH2CH2)(3)N and P(iso-PrNCH2CH2)(3)N},
   volume = {1},
   year = {1995}
}

TY  - JOUR
ID  - 366819
AU  - Wroblewski, A. E. - Pinkas, Jiří - Verkade, J. G.
PY  - 1995
TI  - Strongly basic proazaphosphatranes: P(EtNCH2CH2)(3)N and P(iso-PrNCH2CH2)(3)N
JF  - Main Group Chemistry
VL  - 1
IS  - 1
SP  - 69
EP  - 69
PB  - GORDON BREACH SCI PUBL LTD
SN  - 10241221
KW  - PRO-AZAPHOSPHATRANES
KW  - BOND
KW  - ATRANES
KW  - SYSTEMS
KW  - CRYSTAL
KW  - ATOMS
N2  - 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%.
ER  -

WROBLEWSKI, A. E.; Jiří PINKAS a J. G. VERKADE. Strongly basic proazaphosphatranes: P(EtNCH2CH2)(3)N and P(iso-PrNCH2CH2)(3)N. \textit{Main Group Chemistry}. READING, UK: GORDON BREACH SCI PUBL LTD, 1995, roč.~1, č.~1, s.~69-79. ISSN~1024-1221.

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