Synthesis and Structural Characterisation of [Ir4(CO)8(CH3)(mu4-eta3-Ph2PCCPh)(mu-PPh2)] and of the Carbonylation Product [Ir4(CO)8{C(O)CH3}(mu4-eta3-Ph2PCCPh)(mu-PPh2)]; First Evidence for the Formation of a CO Cluster Adduct before CO Insertion
Abstract:A desprotonação do cluster [(µ-H)Ir4(CO)10(µ-PPh2)], 1, leva à formação de [Ir4(CO)10(µ-PPh2)]que reage com Ph2PCCPh e CH3I para dar [Ir4(CO)8(CH3)(µ4-η 3-Ph2PCCPh)(µ-PPh2)], 2 (34%), além de [Ir4(CO)9(µ3-η 3-Ph2PC(H)CPh)(µ-PPh2)] e [(µ-H)Ir4(CO)9(Ph2PC≡CPh)-(µ-PPh2)]. O composto 2, caracterizado por uma análise de difração de raios-X, contem um arranjo metálico na forma de uma borboleta, com o ligante Ph2PCCPh interagindo com os quatro átomos de Ir e a metila ligada de modo terminal. A carbonilação de 2 resul… Show more
“…In 5, the phosphido bridge is across an open RuÁ Á ÁOs edge and hence the angle at the phosphorus atom is correspondingly large ($106°compared to $75°for 2-4); such a phosphido bridge is rather uncommon [8]. With the exception of 4, in which the hydrides were located from a low angle difference map, the hydride locations were placed by potential energy calculations using the program XHYDEX XHYDEX [9].…”
“…In 5, the phosphido bridge is across an open RuÁ Á ÁOs edge and hence the angle at the phosphorus atom is correspondingly large ($106°compared to $75°for 2-4); such a phosphido bridge is rather uncommon [8]. With the exception of 4, in which the hydrides were located from a low angle difference map, the hydride locations were placed by potential energy calculations using the program XHYDEX XHYDEX [9].…”
“…doi:10.1016/j.jorganchem.2004.08.010 this tetranuclear cluster under thermolytic conditions with C 2 (COOMe) 2 , to yield [Ir 4 (CO) 8 {C 2 (COOMe) 2 } 4 ] [22], and with cod (cod = cyclooctadiene), to give the alkyne containing clusters [Ir 4 (CO) 5 (cod) 2 (C 8 H 10 )] and [Ir 7 -(CO) 12 (cod)(C 8 H 11 )(C 8 H 10 )] [23,24] all in very low yields, and that of the oxidation of [Ir 6 (CO) 15 ] 2À with ferrocinium in the presence of PhCCPh to yield [Ir 6 -(CO) 14 (l 3 -g 2 -HCCPh)] and [Ir 6 (CO) 12 (l 3 -g 2 -HCCPh) 2 ] [25]. The cluster [HIr 4 (CO) 10 (l-PPh 2 )] [26] has proven itself a good entry into tetranuclear iridium organometallic chemistry [27][28][29][30][31][32][33][34][35]. Its derivative [HIr 4 -(CO) 9 (Ph 2 PC"CPh)(l-PPh 2 )] (1) undergoes a selective rearrangement under mild conditions to give [Ir 4 -(CO) 8 (l 3 -g 2 -HCCPh)(l-PPh 2 ) 2 ] (2) [34].…”
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