Producción Científica Profesorado

Reactivity and structural patterns of phenylphosphines in acetylene and acetylide carbonyl trinuclear ruthenium clusters



Sánchez Cabrera, Gloria

2019

Erik G. Rojo-Gómeza, Abril I. Munguía-Lara, Daniel O. González-Abrego, Gloria Sánchez-Cabrera, José G. Alvarado-Rodríguez, María G. Hernández-Cruz, María J. Rosales-Hoz, Marco A. Leyva, Ana L.Carrasco, Noemí Andrade-López, Francisco J. Zuno-Cruz, Reactivity and structural patterns of phenylphosphines in acetylene and acetylide carbonyl trinuclear ruthenium clusters, Polyhedron 161 (2019) 251-260


Abstract


The acetylene [Ru3(?-CO)(CO)9{3-?2-(//)HCCR}] (1a: R?=?C(Me)CH2); 1b: and the acetylide [Ru3(-H)(CO)9{3-?2-(?)CCR}] (2a: R?=?C(Me)CH2; 2b: clusters have been synthesized from the reaction of [Ru3(CO)10(NCMe)2] with 2-methyl-1-buten-3-yne and 1-ethynylcyclohexene respectively. The reactions of the corresponding parallel acetylene 1a or 1b with triphenylphosphine or diphenylmethylphosphine yielded four isostructural compounds [Ru3(?-CO)(CO)8(L){3-?2-(//)HCCR}] (3a1: L?=?PPh3, 3a2: L?=?PPh2Me, R?=?C(Me)CH2; 3b1: L?=?PPh3, 3b2: L?=?PPh2Me, where, the alkynes are still coordinated to the metallic fragment as acetylene groups in a ?3-?2 parallel fashion. Also, the isomer compounds [Ru3(-H)(CO)8(L){3-?2-(?)CCR}] (4a1 and 5a1: L?=?PPh3, 4a2 and 5a2: L?=?PPh2Me, R?=?C(Me)CH2; 4b1 and 5b1: L?=?PPh3, 4b2 and 5b2: L?=?PPh2Me, ; and the disubstituted phenylphosphine clusters [Ru3(-H)(CO)7(L)2{3-?2-(?)CCR}] (6a1: L?=?PPh3, 6a2: L?=?PPh2Me, R?=?C(Me)CH2; 6b1: L?=?PPh3, 6b2: L?=?PPh2Me, were formed during each reaction. In these compounds, the parallel-acetylene group undergoes an oxidative addition and a rearrangement of the coordinated organic fragment to a 3-?2 perpendicular coordination mode of the CC axis by breaking acetylene CH bond to give a hydride ligand in each case. The synthesis of clusters [Ru3(?-CO)(CO)8(PPh3){3-?2-(//)HCCC6H22,4,5-Me3}] (3c1), [Ru3((-H)(CO)8(PPh3){3-?2-(?)-CCC6H22,4,5-Me3}] (4c1 and 5c1) and [Ru3(-H)(CO)7(PPh3)2{3-?2-(?)CCC6H22,4,5-Me3}] (6c1) are also described. All compounds have been characterized in solution by infrared spectroscopy and by 1H, 13C{1H} and 31P{1H} NMR. The molecular structures of compounds 2b, 3a1, 3b1, 4a1, 4c1, and 6b1 have been established by single crystal X-ray diffraction studies.



Producto de Investigación




Artículos relacionados

Pyrolysis of [Ru3(CO)10(dppe)]: activation of C?H and P?Ph bonds.: The crystal structure and dynamic...

Monodentate, N-Heterocyclic Carbene-Type Coordination of 2,2?-Bipyridine and 1,10-Phenanthroline to ...

The reaction of [H4Ru4(CO)12] with 1-penten-3-yne: dimerization and trimerization through the triple...

Reactivity of Triosmium Carbonyl Clusters with 1,8-Diaminonaphthalene ? Synthesis and Structural Cha...

The hydrogenation reaction of [Ru3(CO)10(C6F5)2P(CH2)2P(C6F5)2]: Migration of a C6F5 group from a ph...

Reactivity of TpMe2Ir(C2H4)(DMAD) with carboxylic acids. A DFT study on geometrical isomers and stru...

Synthetic, Mechanistic, and Theoretical Studies on the Generation of Iridium Hydride Alkylidene and ...

Metallacyclic Pyridylidene Structures from Reactions of Terminal Pyridylidenes with Alkenes and Acet...

CH and CC bond activations of terminal alkynes in the presence of a butterfly-shaped heteronuclear R...

Understanding and Predicting Distorted T- versus Y-Geometries for Neutral Chromous Complexes Support...