Cyclopentadienylmolybdenum Tricarbonyl Complexes: (η5-C5H5)-Mo(CO)3X

Sazonov, P. K.; Beletskaya, I. P.

doi:10.1002/047084289x.rn01533

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“…The average B–B bond distance in the triborane chain of 2 (1.736 Å) is shorter as compared to the average B–B bond distance of [B 3 H 7 Fe 2 (CO) 6 ] (1.778 Å) and [1,2-(Cp*Ru) 2 B 3 H 7 (μ-H) 2 ] (1.920 Å) . The Mo–Mo bond distance of 3.0326(6) Å is analogous to that of [{Cp(CO) 2 Mo} 2 {μ–η 2 :η 2 -P 2 }] (3.036(2) Å); however, it is shorter than that of [CpMo(CO) 3 ] 2 (3.235 Å), [Mo 2 (CO) 10 ] 2– (3.123(7) Å), and [(Cp*MoCl) 2 B 3 H 7 ], I (3.095(12) Å) . In addition to the Cp* ligand, both the Mo centers are ligated to one CO ligand.…”

Section: Resultsmentioning

confidence: 94%

Structures and Bonding of Early Transition Metallaborane Clusters

et al. 2022

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Structures and bonding of various homo and heterometallic metallaborane clusters are described which are stabilized in the coordination sphere of early transition metals. For example, the bimetallic triborane species, [{Cp*Mo(CO)}2{µη 3 :η 3 -B3H7}], 2 has been synthesized from the pyrolysis of an in situ generated intermediate, produced from the reaction of [Cp*Mo(CO)3Me], 1 and [LiBH4•THF], with an excess amount of [BH3•THF]. Superficially cluster 2 is isostructural but not isoelectronic with [(Cp*MoCl)2B3H7] (I). Both clusters 2 and I contain a bimetallic template bridged by {B3H7} moiety. Cluster 2 is denoted as a unique saturated and unsubstituted closo bimetallic B3H7 cluster. Theoretical output implies that saturation in such clusters brings thermodynamic stability. Further, we have developed a new strategy for the synthesis of various heterometallic metal-rich metallaborane clusters. For example, pyrolysis of an intermediate, obtained from the reaction of [Cp*MoCl4], 4 and [LiBH4•THF], with cobalt and iron carbonyl compounds yielded triply bridging hydrido(hydroborylene), [{Cp*Mo(CO)2}2Co(CO)3BH(μ-H)], 5, tetrametallic μ4-boride, [{Cp*Mo(CO)2}2(μ4-B)(μ-H){Co2(CO)5}], 6, triple decker complex, [(Cp*Mo)2{µ-η 6 :η 6 -B4H4Co2(CO)5}(μ-H)2], 7, metal-rich dimolybdaborane cluster, [(Cp*Mo)2Co2(CO)3(μ-CO)3B3H3(μ-H)2], 8 and mixed-metal cluster, [(Cp*Mo)2B4H8Fe(CO)3], 9. All the molecules have been characterized by 1 H, 11 B{ 1 H}, and 13 C{ 1 H} NMR spectroscopy; mass spectrometry; infrared (IR) spectroscopy and single-crystal X-ray diffraction studies for clusters 2 and 5-9. The electron counting rules and density functional theory (DFT) calculations provided further insight into the bonding and electronic structures of these clusters.

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