Reactivity of a (η5-phospholyl) cobalt dicarbonyl complex. Synthesis of [Co2(η5-PC4H2tBu 2)2(CO)2] and [Co2(η5-PC4H2tBu 2)2(η-CHCO2Et)(CO)2]

Andrew J.M. Caffyn; Duncan Carmichael; Françis Mathey; Louis Ricard

doi:10.1021/om9606855

Reactivity of a (η⁵-phospholyl) cobalt dicarbonyl complex. Synthesis of [Co₂(η⁵-PC₄H₂^tBu ₂)₂(CO)₂] and [Co₂(η⁵-PC₄H₂^tBu ₂)₂(η-CHCO₂Et)(CO)₂]

Andrew J.M. Caffyn
, Duncan Carmichael
, Françis Mathey
, Louis Ricard

CNRS

Research output: Contribution to journal › Article › peer-review

Abstract

Thermolysis of 2,2′,5,5′-tetra-tert-butyl-1,1′-biphosphole with Co₂(CO)_s gives good yields of (2,5-di-tert-butylphospholyl)dicarbonylcobalt (1), a compound which provided access to a range of cobalt phospholyl complexes. Thermolysis with trimethyl phosphite produced C₁₂H₂₀PCo(CO)P(OMe)₃ (2), while photolysis with 1,3-cyclohexadiene and 1,5-cyclooctadiene gave the corresponding complexes C₁₂H₂₀PCo(diene) (3, 4). In the absence of a donor ligand, a metal-metal doubly bridged dimer 6 was obtained; this reacted classically with ethyl diazoacetate to give the bridging complex {C₁₂H₂₀PCo(CO)}₂(μ-CHCO₂Et) (7). Prolonged heating of 1 with 3-hexyne in xylene gave the cyclotrimerization product C₆Et₆; an initial attempt to prepare pyridines by cocyclization of PrCN with PhC=CH gave the cyclobutadiene complex C₁₂H₂₀PCo(1,2-C₄H₂Ph₂) (5).

Original language	English
Pages (from-to)	2049-2054
Number of pages	6
Journal	Organometallics
Volume	16
Issue number	10
DOIs	https://doi.org/10.1021/om9606855
Publication status	Published - 1 Jan 1997
Externally published	Yes

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@article{69dc88d986df413d9452f7dbf0caa338,

title = "Reactivity of a (η5-phospholyl) cobalt dicarbonyl complex. Synthesis of [Co2(η5-PC4H2tBu 2)2(CO)2] and [Co2(η5-PC4H2tBu 2)2(η-CHCO2Et)(CO)2]",

abstract = "Thermolysis of 2,2′,5,5′-tetra-tert-butyl-1,1′-biphosphole with Co2(CO)s gives good yields of (2,5-di-tert-butylphospholyl)dicarbonylcobalt (1), a compound which provided access to a range of cobalt phospholyl complexes. Thermolysis with trimethyl phosphite produced C12H20PCo(CO)P(OMe)3 (2), while photolysis with 1,3-cyclohexadiene and 1,5-cyclooctadiene gave the corresponding complexes C12H20PCo(diene) (3, 4). In the absence of a donor ligand, a metal-metal doubly bridged dimer 6 was obtained; this reacted classically with ethyl diazoacetate to give the bridging complex \{C12H20PCo(CO)\}2(μ-CHCO2Et) (7). Prolonged heating of 1 with 3-hexyne in xylene gave the cyclotrimerization product C6Et6; an initial attempt to prepare pyridines by cocyclization of PrCN with PhC=CH gave the cyclobutadiene complex C12H20PCo(1,2-C4H2Ph2) (5).",

author = "Caffyn, \{Andrew J.M.\} and Duncan Carmichael and Fran{\c c}is Mathey and Louis Ricard",

year = "1997",

month = jan,

day = "1",

doi = "10.1021/om9606855",

language = "English",

volume = "16",

pages = "2049--2054",

journal = "Organometallics",

issn = "0276-7333",

number = "10",

}

TY - JOUR

T1 - Reactivity of a (η5-phospholyl) cobalt dicarbonyl complex. Synthesis of [Co2(η5-PC4H2tBu 2)2(CO)2] and [Co2(η5-PC4H2tBu 2)2(η-CHCO2Et)(CO)2]

AU - Caffyn, Andrew J.M.

AU - Carmichael, Duncan

AU - Mathey, Françis

AU - Ricard, Louis

PY - 1997/1/1

Y1 - 1997/1/1

N2 - Thermolysis of 2,2′,5,5′-tetra-tert-butyl-1,1′-biphosphole with Co2(CO)s gives good yields of (2,5-di-tert-butylphospholyl)dicarbonylcobalt (1), a compound which provided access to a range of cobalt phospholyl complexes. Thermolysis with trimethyl phosphite produced C12H20PCo(CO)P(OMe)3 (2), while photolysis with 1,3-cyclohexadiene and 1,5-cyclooctadiene gave the corresponding complexes C12H20PCo(diene) (3, 4). In the absence of a donor ligand, a metal-metal doubly bridged dimer 6 was obtained; this reacted classically with ethyl diazoacetate to give the bridging complex {C12H20PCo(CO)}2(μ-CHCO2Et) (7). Prolonged heating of 1 with 3-hexyne in xylene gave the cyclotrimerization product C6Et6; an initial attempt to prepare pyridines by cocyclization of PrCN with PhC=CH gave the cyclobutadiene complex C12H20PCo(1,2-C4H2Ph2) (5).

AB - Thermolysis of 2,2′,5,5′-tetra-tert-butyl-1,1′-biphosphole with Co2(CO)s gives good yields of (2,5-di-tert-butylphospholyl)dicarbonylcobalt (1), a compound which provided access to a range of cobalt phospholyl complexes. Thermolysis with trimethyl phosphite produced C12H20PCo(CO)P(OMe)3 (2), while photolysis with 1,3-cyclohexadiene and 1,5-cyclooctadiene gave the corresponding complexes C12H20PCo(diene) (3, 4). In the absence of a donor ligand, a metal-metal doubly bridged dimer 6 was obtained; this reacted classically with ethyl diazoacetate to give the bridging complex {C12H20PCo(CO)}2(μ-CHCO2Et) (7). Prolonged heating of 1 with 3-hexyne in xylene gave the cyclotrimerization product C6Et6; an initial attempt to prepare pyridines by cocyclization of PrCN with PhC=CH gave the cyclobutadiene complex C12H20PCo(1,2-C4H2Ph2) (5).

U2 - 10.1021/om9606855

DO - 10.1021/om9606855

M3 - Article

AN - SCOPUS:0000054263

SN - 0276-7333

VL - 16

SP - 2049

EP - 2054

JO - Organometallics

JF - Organometallics

IS - 10

ER -

Reactivity of a (η5-phospholyl) cobalt dicarbonyl complex. Synthesis of [Co2(η5-PC4H2tBu 2)2(CO)2] and [Co2(η5-PC4H2tBu 2)2(η-CHCO2Et)(CO)2]

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Reactivity of a (η⁵-phospholyl) cobalt dicarbonyl complex. Synthesis of [Co₂(η⁵-PC₄H₂^tBu ₂)₂(CO)₂] and [Co₂(η⁵-PC₄H₂^tBu ₂)₂(η-CHCO₂Et)(CO)₂]