Addition of a Terminal Phosphinidene Complex to Norbornadiene

Jui Te Hung; Pooran Chand; Frank R. Fronczek; Stephen F. Watkins; Koop Lammertsma

doi:10.1021/om00028a065

Addition of a Terminal Phosphinidene Complex to Norbornadiene

Jui Te Hung, Pooran Chand, Frank R. Fronczek, Stephen F. Watkins, Koop Lammertsma

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16 Citations (Scopus)

Abstract

The phosphinidene complex Ph-P-W(CO)₅ (2), generated from the appropriate 7-phosph-anorbornadiene complex 1, reacts with norbornadiene to give a mixture of (Z)-exo, (Z)-endo, (E)-exo, and (E)-endo 1,2-addition products. The ratio of these Z/E and exo/endo phosphiranes is 2 and 10, respectively. X-ray analysis shows the major isomer to be the sterically congested (Z)-exo-phosphirane 3, which crystallizes in the orthorhombic space group P2₁2₁2₁ with cell dimensions a = 6.534(2) Å, b = 13.663(2) Å, c = 20.555(2) Å, V = 1835(1) Å³, and Z = 4; the structure was refined to R = 0.0252 and R_w = 0.0272 for 3167 reflections with I > 2.5σ(I) and 227 paramters. The stereochemistry and reactivity of phosphinidene complex 2 toward norbornadiene and the stabilizing conjugative features in the resulting phosphiranes are discussed.

Original language	English
Pages (from-to)	1401-1405
Number of pages	5
Journal	Organometallics
Volume	12
Issue number	4
DOIs	https://doi.org/10.1021/om00028a065
Publication status	Published - 1993
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{6a0ec354b02b4845b771e82365fbda0f,

title = "Addition of a Terminal Phosphinidene Complex to Norbornadiene",

abstract = "The phosphinidene complex Ph-P-W(CO)5 (2), generated from the appropriate 7-phosph-anorbornadiene complex 1, reacts with norbornadiene to give a mixture of (Z)-exo, (Z)-endo, (E)-exo, and (E)-endo 1,2-addition products. The ratio of these Z/E and exo/endo phosphiranes is 2 and 10, respectively. X-ray analysis shows the major isomer to be the sterically congested (Z)-exo-phosphirane 3, which crystallizes in the orthorhombic space group P212121 with cell dimensions a = 6.534(2) {\AA}, b = 13.663(2) {\AA}, c = 20.555(2) {\AA}, V = 1835(1) {\AA}3, and Z = 4; the structure was refined to R = 0.0252 and Rw = 0.0272 for 3167 reflections with I > 2.5σ(I) and 227 paramters. The stereochemistry and reactivity of phosphinidene complex 2 toward norbornadiene and the stabilizing conjugative features in the resulting phosphiranes are discussed.",

author = "Hung, {Jui Te} and Pooran Chand and Fronczek, {Frank R.} and Watkins, {Stephen F.} and Koop Lammertsma",

year = "1993",

doi = "10.1021/om00028a065",

language = "English",

volume = "12",

pages = "1401--1405",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "4",

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TY - JOUR

T1 - Addition of a Terminal Phosphinidene Complex to Norbornadiene

AU - Hung, Jui Te

AU - Chand, Pooran

AU - Fronczek, Frank R.

AU - Watkins, Stephen F.

AU - Lammertsma, Koop

PY - 1993

Y1 - 1993

N2 - The phosphinidene complex Ph-P-W(CO)5 (2), generated from the appropriate 7-phosph-anorbornadiene complex 1, reacts with norbornadiene to give a mixture of (Z)-exo, (Z)-endo, (E)-exo, and (E)-endo 1,2-addition products. The ratio of these Z/E and exo/endo phosphiranes is 2 and 10, respectively. X-ray analysis shows the major isomer to be the sterically congested (Z)-exo-phosphirane 3, which crystallizes in the orthorhombic space group P212121 with cell dimensions a = 6.534(2) Å, b = 13.663(2) Å, c = 20.555(2) Å, V = 1835(1) Å3, and Z = 4; the structure was refined to R = 0.0252 and Rw = 0.0272 for 3167 reflections with I > 2.5σ(I) and 227 paramters. The stereochemistry and reactivity of phosphinidene complex 2 toward norbornadiene and the stabilizing conjugative features in the resulting phosphiranes are discussed.

AB - The phosphinidene complex Ph-P-W(CO)5 (2), generated from the appropriate 7-phosph-anorbornadiene complex 1, reacts with norbornadiene to give a mixture of (Z)-exo, (Z)-endo, (E)-exo, and (E)-endo 1,2-addition products. The ratio of these Z/E and exo/endo phosphiranes is 2 and 10, respectively. X-ray analysis shows the major isomer to be the sterically congested (Z)-exo-phosphirane 3, which crystallizes in the orthorhombic space group P212121 with cell dimensions a = 6.534(2) Å, b = 13.663(2) Å, c = 20.555(2) Å, V = 1835(1) Å3, and Z = 4; the structure was refined to R = 0.0252 and Rw = 0.0272 for 3167 reflections with I > 2.5σ(I) and 227 paramters. The stereochemistry and reactivity of phosphinidene complex 2 toward norbornadiene and the stabilizing conjugative features in the resulting phosphiranes are discussed.

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U2 - 10.1021/om00028a065

DO - 10.1021/om00028a065

M3 - Article

AN - SCOPUS:0001506358

SN - 0276-7333

VL - 12

SP - 1401

EP - 1405

JO - Organometallics

JF - Organometallics

IS - 4

ER -

Addition of a Terminal Phosphinidene Complex to Norbornadiene

Abstract

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