Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters

0421812 - ÚACH 2014 RIV CH eng J - Journal Article
Bould, Jonathan - Londesborough, Michael Geoffrey Stephen - Kennedy, JD. - Macias, R. - Winter, REK. - Císařová, I. - Kubát, Pavel - Lang, Kamil
Isonitrile ligand effects on small-molecule-sequestering in bimetalladodecaborane clusters.
Journal of Organometallic Chemistry. Roč. 747, december (2013), s. 76-84. ISSN 0022-328X. E-ISSN 1872-8561
R&D Projects: GA ČR GAP207/11/1577; GA ČR GAP208/10/1678; GA ČR GAP207/11/0705
Institutional support: RVO:61388980 ; RVO:61388955
Keywords : Metallaboranes * Small molecule * Sequestration * DFT * Isonitrile * Carbon monoxide
Subject RIV: CA - Inorganic Chemistry; CF - Physical ; Theoretical Chemistry (UFCH-W)
Impact factor: 2.302, year: 2013

The bimetalladodecaborane cluster compound [(PMe2Ph)(4)Pt2B10H10] 1, quantitatively reacts with EtNC at room temperature to afford [{(EtNC)(PMe2Ph)(3)}(mu-EtNC) Pt2B10H10] 3 in which one molecule of EtNC replaces a terminal PMe2Ph ligand, and a second molecule of EtNC bridges the PtePt vector. The metalbridging EtNC molecule can be ejected from 3, either by irradiation with UV light, or via displacement with CO to form [{(EtNC)(PMe2Ph)(3)}(mu-CO) Pt2B10H10] 4. The CO-bridge may then in turn be replaced with SO2 to give [{(EtNC)(PMe2Ph)(3)}(mu-SO2) Pt2B10H10] 5. If 3 is allowed to react directly with SO2 then the SO2 molecule takes up a bridging position and the bridging EtNC displaces a terminal metal-bound phosphine to afford [{(EtNC)(2)(PMe2Ph)(2)}(mu-SO2) Pt2B10H10] 6. The transient absorption spectrum of 3 under UV illumination is investigated and shows that the bridging isonitrile is ejected to produce a transient spectrum very similar to that of [(PMe2Ph)(4)Pt2B10H10] 1. Reaction of [(PMe2Ph)(4)Pd2B10H10] 7, viz. the dipalladium analogue of 1, with EtNC results in the displacement of two PMe2Ph phosphine ligands forming [{(EtNC)(2)(PMe2Ph)(2)} Pd2B10H10] 8, which has no bridging EtNC unit and which shows only a weak ability to form an adduct with SO2. DFT calculations at the B3LYP/6-31G* level mirror the observed data well.
Permanent Link: http://hdl.handle.net/11104/0228072