659728-41-3Relevant academic research and scientific papers
Reactions of the dianion [1,1,1-(CO)3-2-Ph-closo-1,2-MnCB 9H9]2- with transition-metal cations: Facile insertion and then extrusion of cluster vertexes
Du, Shaowu,Jeffery, John C.,Kautz, Jason A.,Xiu, Lian Lu,McGrath, Thomas D.,Miller, Thomas A.,Riis-Johannessen,Stone, F. Gordon A.
, p. 2815 - 2825 (2008/10/09)
The manganacarborane dianion in [N(PPh3)2][NEt 4][1,1,1-(CO)3-2-Ph-closo-1,2-MnCB9H 9] (1b) reacts with cationic transition metal-ligand fragments to give products in which the electrophilic metal groups (M′) are exo-polyhedrally attached to the {closo-1,2-MnCB9} cage system via three-center two-electron B-H → M′ linkages and generally also by Mn-M′ bonds. With {Cu(PPh3)}+, the Cu-Mn-Cu trimetallic species [1,6-{Cu(PPh3)}-1,7-{Cu(PPh3)}-6,7- (μ-H)2-1,1,1-(CO)3-2-Ph-closo-1,2-MnCB 9H7] (3a) is formed, whereas reactions with {M′(dppe)}2+ (M′ = Ni, Pd; dppe = Ph2PCH 2CH2PPh2) give [1,3-{Ni(dppe)}-3-(μ-H)-1,1, 1-(CO)3-2-Ph-closo1,2-MnCB9H8] (5a) and [1,3,6-{Pd(dppe)}-3,6-(μ-H)2-1,1,1-(CO)3-2-Ph-closo1,2- MnCB9H7] (5b), both of which contain M′-Mn bonds. The latter reaction with M′ = Pt affords [3,6-{Pt(dppe)}-3,6-(μ-H) 2-1,1,1-(CO)3-2-Ph-closo-1,2-MnCB9H 7] (6), which lacks a Pt-Mn connectivity. Compound 6 itself spontaneously converts to [1-Ph-2,2,2-(CO)3-8,8-(dppe)-hypercloso-8, 2,1-PtMnCB9H9] (7b) and thence to [3,6,7-{Mn(CO) 3}-3,7-(μ-H)2-1-Ph-6,6-(dppe)-closo-6,1-PtCB 8H6] (8). This sequence occurs via initial insertion of the {Pt(dppe)} unit and then extrusion of {Mn(CO)3} and one {BH} vertex. In the presence of alcohols ROH, compound 6 is transformed to the 7-OR substituted analogues of 7b. X-ray diffraction studies were essential in elucidating the structures encountered in compounds 5-8 and hence in understanding their behavior.
