Transformation of an η1-coordinated phosphaalkyne into a bridging phosphinidene ligand

The phosphinidene-bridged complexes [Mo 2 Cp(μ-κ 1 :κ 1 ,η 5 -PC 5 H 4 )(CO) 2 L] and [Mo 2 Cp 2 (μ-PH)-(CO) 2 L] (Cp = η 5 -C 5 H 5 ; L=η 6 -1,3,5-C 6 H 3 t Bu 3 ) react readily with [Fe 2 (CO) 9 ] or the solvate complexes [M(CO) 5 (THF)] (M=Cr, Mo, W; THF=tetrahydrofuran) to give, as a result of the addition of the corresponding 16-electron M(CO) n fragments to their multiple Mo-P bonds, the trinuclear derivatives [FeMo 2 Cp(μ 3 -κ 1 :κand [MMo 2 Cp 2 (μ 3 -PH)(CO) 7 L]. The PH-bridged complexes display a distorted tetrahedral environment around their P atom, according to X-ray diffraction studies on the Fe, Cr, and W compounds, whereas the PC 5 H 4 -bridged ones display an unusual trigonalpyramidal geometry around the P atoms (sum of M-P-M angles 359.6°for the Fe compound). The latter species were stable toward hydrolysis, whereas the trinuclear PH-bridged complexes underwent easy hydrolysis of their P-Mo(metallocene) bonds to give the corresponding PH 2 -bridged derivatives [FeMoCp(μ-PH 2 )(CO) 6 L] and [MMoCp(μ-PH 2 )(CO) 7 L] (M=Cr, Mo, W). § This paper is dedicated to the memory of Dr. J. Manuel Concell on, former dean of the School of Chemistry and distinguished professor of organic chemistry at the Universidad de Oviedo.

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Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo₂Cp(μ-κ¹:κ¹,η⁵-PC₅H₄)(CO)₂L] and [Mo₂Cp₂(μ-PH)(CO)₂L] (L = η⁶-1,3,5-C₆H₃^tBu₃)

Alvarez

Amor

Garcı́a

et al. 2010

Organometallics

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Transformation of an η1-coordinated phosphaalkyne into a bridging phosphinidene ligand

Cited by 1 publication

References 30 publications

Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo₂Cp(μ-κ¹:κ¹,η⁵-PC₅H₄)(CO)₂L] and [Mo₂Cp₂(μ-PH)(CO)₂L] (L = η⁶-1,3,5-C₆H₃^tBu₃)

Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo₂Cp(μ-κ¹:κ¹,η⁵-PC₅H₄)(CO)₂L] and [Mo₂Cp₂(μ-PH)(CO)₂L] (L = η⁶-1,3,5-C₆H₃^tBu₃)

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Transformation of an η1-coordinated phosphaalkyne into a bridging phosphinidene ligand

Cited by 1 publication

References 30 publications

Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2L] and [Mo2Cp2(μ-PH)(CO)2L] (L = η6-1,3,5-C6H3tBu3)

Structure, Bonding, and Reactivity of Binuclear Complexes Having Asymmetric Trigonal Phosphinidene Bridges: Addition of 16-Electron Metal Carbonyl Fragments to the Dimolybdenum Compounds [Mo2Cp(μ-κ1:κ1,η5-PC5H4)(CO)2L] and [Mo2Cp2(μ-PH)(CO)2L] (L = η6-1,3,5-C6H3tBu3)

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