ic060318d_si_003.cif (18.92 kB)
Comparative Bonding Behavior of Functional Cyclopentadienyl Ligands and Boron-Containing Analogues in Heterometallic Complexes and Clusters†
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posted on 2006-07-24, 00:00 authored by Pierre Croizat, Nicolas Auvray, Pierre Braunstein, Richard WelterThe reactivity of isolobal molybdenum carbonylmetalates containing a 2-boratanaphthalene, [Mo(η5-2,4-MeC9H6BMe)(CO)3]- (5a) and [Mo(η5-2,4-MeC9H6BNi-Pr2)(CO)3]- (5b), a 1-boratabenzene, [Mo(η5-3,5-Me2C5H3BNi-Pr2)(CO)3]- (8), or a functionalized cyclopentadienyl ligand, the new metalate [Mo(η5-C5H4Ph)(CO)3]- (7) and [Mo(η5-C5H4NMe2)(CO)3]- (9), toward palladium (I and II) or platinum (I and II) complexes, such as trans-[PdCl2(NCPh)2],
[Pd2(NCMe)6](BF4)2, trans-[PtCl2(PEt3)2], and [N(n-Bu)4]2 [Pt2Cl4(CO)2], has been investigated, and this has allowed
an evaluation of the influence of the π-bonded ligands on the structures and unprecedented coordination modes
observed in the resulting metal−metal-bonded heterometallic clusters. The new 58 CVE planar-triangulated
centrosymmetric clusters, [Mo2Pd2(η5-C5H4Ph)2(CO)6(PEt3)2] (11), [Mo2Pd2(η5-2,4-MeC9H6BNi-Pr2)2(CO)6] (12), [Mo2Pd2(η5-3,5-Me2C5H3BNi-Pr2)2(CO)6] (13), [Mo2Pd2(η5-C5H4NMe2)2(CO)6(PEt3)2] (15), [Mo2Pt2(η5-C5H4NMe2)2(CO)6(PEt3)2] (16), and [Mo2Pt2(η5-C5H4NMe2)2(CO)8] (20), have been characterized by single-crystal X-ray diffraction.
Their structural features were compared with those of the 54 CVE cluster [Re2Pd2(η5-C4H4BPh)2(CO)6)] (4), previously
obtained from the borole-containing metalate [Re(η5-C4H4BPh)(CO)3]- (2), in which a 2e−3c B−Cipso−Pd interaction
involving the π-ring was observed. As an extension of what has been observed in 4, clusters 12 and 13 present
a direct interaction of the boratanaphthalene (12) and the boratabenzene (13) ligands with palladium. In clusters
11, 15, 16, and 20, the π-ring does not interact with the palladium (11 and 15) or platinum centers (16 and 20),
which confers to these clusters a geometry very similar to that of [Mo2Pd2(η5-C5H5)2(CO)6(PEt3)2] (3b). The
carbonylmetalates [Mo(π-ring)(CO)3]- are thus best viewed as formal four electron donors which bridge a dinuclear
d9−d9 unit. The orientation of this building block in the clusters influences the shape of their metal cores and the
bonding mode of the bridging carbonyl ligands. The crystal structure of new centrosymmetric complex [Mo(η5-C5H4Ph)(CO)3]2 (10) was determined, and it revealed intramolecular contacts of 2.773(4) Å between the carbon
atoms of carbonyl groups across the metal−metal bond and intermolecular bifurcated interactions between the
carbonyl oxygen atoms (2.938(4) and 3.029(4) Å), as well as intermolecular C−H···πAr(CC) interactions (2.334(3) and 2.786(4) Å) involving the phenyl substituents.
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intramolecular contactsPt 2ClHeterometallic Complexesbuilding block2Pdphenyl substituentscarbon atomscoordination modesIIfunctionalized cyclopentadienyl ligandclusters influencesisolobal molybdenum carbonylmetalates54 CVE clustermetal coresComparative Bonding BehaviorFunctional Cyclopentadienyl Ligandscarbonyl groupscrystal structureelectron donorscarbonyl ligandsMo
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