Metal‐Rich Metallaboranes: Synthesis, Structure, and Bonding of Heteronuclear Trimetallic Clusters containing (μ3‐BH) Ligand.

Building upon our earlier results on the chemistry of nido‐1,2‐[(Cp*RuH)2B3H7] (Cp*=ɳ5‐C5Me5) (nido‐1) with different transition metal carbonyls, we continued to investigate the reactivity with group 7 metal carbonyls under photolytic condition. Photolysis of nido‐1 with [Mn2(CO)10] led to the isolation of a trimetallic [(Cp*Ru)2{Mn(CO)3}(μ‐H)(μ‐CO)3(μ3‐BH)] (2) cluster with a triply bridging borylene moiety. Cluster 2 is a rare example of a tetrahedral cluster having hydrido(hydroborylene) moiety. In an attempt to synthesize the Re analogue of 2, a similar reaction was carried out with [Re2(CO)10] that yielded the trimetallic [(Cp*Ru)2{Re(CO)3}(μ‐H)(μ‐CO)3(μ3‐BH)] (3) cluster having a triply bridging borylene unit. Along with 3, a trimetallic square pyramid cluster [(Cp*Ru)2{Re(CO)3}(μ‐H)2(μ‐CO)(μ3,ɳ2‐B2H5)] (4), and heterotrimetallic hydride clusters [{Cp*Ru(CO)2}‐{Re(CO)4}2(μ‐H)] (5) and [{Cp*Ru(CO)}{Re(CO)4}2(μ‐H)3] (6) were isolated. Cluster 4 is a unique example of a M2M′B2 cluster having diboron capped Ru2Re‐triangle. The hydride clusters 5 and 6 have triangular RuRe2 frameworks with one and three μ‐Hs respectively. All the clusters have been characterized by using mass spectrometry, 1H, 11B{1H}, 13C{1H} NMR and IR spectroscopies analyses and the structures of clusters 2–6 have been unambiguously established by XRD analyses. Furthermore, to understand the electronic, structural, and bonding features of the synthesized metal‐rich clusters, DFT calculations have been performed. [ABSTRACT FROM AUTHOR]