Rearrangement of a W(CO)5-complexed 7-phosphanorbornadiene analyzed by ab initio MO calculations

Bing Wang; Charles H. Lake; Koop Lammertsma

doi:10.1021/om9703649

Rearrangement of a W(CO)5-complexed 7-phosphanorbornadiene analyzed by ab initio MO calculations

Bing Wang, Charles H. Lake, Koop Lammertsma

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9 Citations (Scopus)

Abstract

The rearrangement of W(CO)₅-complexed 7-phosphanorbornadiene 1 to the 7-phosphatricyclo [3.2.0^4,6]hept-2-ene complex 2 is investigated experimentally and with the aid of ab initio theory at MP2(fc)/6-31G*. Photochemical concerted and thermal biradical pathways are considered. Calculations on the uncomplexed parent system indicate that a thermal rearrangement is unlikely because of its 6.4 kcal/mol endothermicity. The relationship of the 1→2 rearrangement with the CuCl-catalyzed, thermal decomposition of 1 to generate the incipient phosphinidene complex PhPW(CO)₅ is discussed.

Original language	English
Pages (from-to)	4145-4149
Number of pages	5
Journal	Organometallics
Volume	16
Issue number	19
DOIs	https://doi.org/10.1021/om9703649
Publication status	Published - 16 Sept 1997
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Rearrangement of a W(CO)5-complexed 7-phosphanorbornadiene analyzed by ab initio MO calculations",

abstract = "The rearrangement of W(CO)5-complexed 7-phosphanorbornadiene 1 to the 7-phosphatricyclo [3.2.04,6]hept-2-ene complex 2 is investigated experimentally and with the aid of ab initio theory at MP2(fc)/6-31G*. Photochemical concerted and thermal biradical pathways are considered. Calculations on the uncomplexed parent system indicate that a thermal rearrangement is unlikely because of its 6.4 kcal/mol endothermicity. The relationship of the 1→2 rearrangement with the CuCl-catalyzed, thermal decomposition of 1 to generate the incipient phosphinidene complex PhPW(CO)5 is discussed.",

author = "Bing Wang and Lake, {Charles H.} and Koop Lammertsma",

year = "1997",

month = sep,

day = "16",

doi = "10.1021/om9703649",

language = "English",

volume = "16",

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journal = "Organometallics",

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T1 - Rearrangement of a W(CO)5-complexed 7-phosphanorbornadiene analyzed by ab initio MO calculations

AU - Wang, Bing

AU - Lake, Charles H.

AU - Lammertsma, Koop

PY - 1997/9/16

Y1 - 1997/9/16

N2 - The rearrangement of W(CO)5-complexed 7-phosphanorbornadiene 1 to the 7-phosphatricyclo [3.2.04,6]hept-2-ene complex 2 is investigated experimentally and with the aid of ab initio theory at MP2(fc)/6-31G*. Photochemical concerted and thermal biradical pathways are considered. Calculations on the uncomplexed parent system indicate that a thermal rearrangement is unlikely because of its 6.4 kcal/mol endothermicity. The relationship of the 1→2 rearrangement with the CuCl-catalyzed, thermal decomposition of 1 to generate the incipient phosphinidene complex PhPW(CO)5 is discussed.

AB - The rearrangement of W(CO)5-complexed 7-phosphanorbornadiene 1 to the 7-phosphatricyclo [3.2.04,6]hept-2-ene complex 2 is investigated experimentally and with the aid of ab initio theory at MP2(fc)/6-31G*. Photochemical concerted and thermal biradical pathways are considered. Calculations on the uncomplexed parent system indicate that a thermal rearrangement is unlikely because of its 6.4 kcal/mol endothermicity. The relationship of the 1→2 rearrangement with the CuCl-catalyzed, thermal decomposition of 1 to generate the incipient phosphinidene complex PhPW(CO)5 is discussed.

UR - http://www.scopus.com/inward/record.url?scp=0000407291&partnerID=8YFLogxK

U2 - 10.1021/om9703649

DO - 10.1021/om9703649

M3 - Article

AN - SCOPUS:0000407291

SN - 0276-7333

VL - 16

SP - 4145

EP - 4149

JO - Organometallics

JF - Organometallics

IS - 19

ER -

Rearrangement of a W(CO)5-complexed 7-phosphanorbornadiene analyzed by ab initio MO calculations

Abstract

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