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A combined experimental and theoretical study of bimetallic bis- and tris-homocubane analogues

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Abstract

Synthesis of various metal-incorporated bis- and tris-homocubane analogues has been reported. Room temperature reactions of [Cp*MCl2]2 (Cp* = η5-C5Me5, M = Ir or Rh) with chalcogenated borohydride reagents, Li[BH2E3] (E = S or Se), yielded a series of bimetallic bis- and tris-homocubane derivatives (1–7). The bishomocubane analogues belong to the 1,3-bishomocubane family with the general formula [(Cp*M)2(μ-E)23-E)43-BH)2] (1: M = Ir, E = S; 2: M = Ir, E = Se; 5: M = Rh, E = S and 6: M = Rh, E = Se), and [(Cp*Ir)2(μ-S)23-S)4(μ-BH2)2], 3, can be described as an unusual bishomocubane having two (μ-BH2) units with a missing-bond. In addition to these bishomocubanes, two trishomocubane derivatives [(Cp*M)2(μ-E)33-E)43-BH)2] (4: M = Ir, E = S and 7: M = Rh, E = Se) were isolated from the above reactions. Trishomocubane 4 adopts a 1,2,4-trishomocubyl structure, whereas 7 is a D3-trishomocubyl analogue. In a similar fashion, thermolysis of [Cp*CoCl]2 with Li[BH2E3] (E = S or Se) led to the formation of Co-1,3-bishomocubane analogues, [(Cp*Co)2(μ-E)23-E)43-BH)2] (8: E = S and 9: E = Se). All the compounds were characterized by multinuclear NMR and IR spectroscopies and mass spectrometric analysis. The core geometries of 1–4 and 8 were unequivocally established by single-crystal X-ray diffraction studies. Density functional theory (DFT) computations further demonstrated that metals and chalcogen atoms play an important role in determining the thermodynamic stability of the bis- and tris-homocubane species.

Graphical abstract: A combined experimental and theoretical study of bimetallic bis- and tris-homocubane analogues

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Publication details

The article was received on 11 Oct 2019, accepted on 27 Nov 2019 and first published on 27 Nov 2019


Article type: Paper
DOI: 10.1039/C9NJ05117A
New J. Chem., 2020, Advance Article

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    A combined experimental and theoretical study of bimetallic bis- and tris-homocubane analogues

    B. Joseph, R. Prakash, K. Pathak, T. Roisnel, S. Kahlal, J. Halet and S. Ghosh, New J. Chem., 2020, Advance Article , DOI: 10.1039/C9NJ05117A

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