Metallacarborane diene π-complexes. I. Synthesis of rhodacarboranes with a η2,η3-2-methylenenorbornadienyl ligand at the rhodium vertex

Large-cage (11–13-vertex) dicarbon metallacarboranes of platinum metals with mono- and polycyclic diolefin ligands

“…Among these compounds are new representatives of closo-( 4 -COD)rhodacarboranes 18(d-f: d, R = CH 2 OH, R 1 = H [14]; e, R = CH CH 2 , R 1 = H; f, R = C(CH 3 ) CH 2 , R 1 = H [15]) and the related complexes with 2-R -NBD ligands, [PPN] [3,3-{ 4 -(NBD-2-R )}-1-R-2-R 1 -3,1,2-closo-RhC 2 B 9 H 9 ] (21a-k: a, R = H, R = R 1 = CH 3 [16]; b, R = CH 2 OH, R = R 1 = H; c, R = CHO, R = R 1 = CH 3 ; d, R = CH 2 OH, R = R 1 = CH 3 ; e, R = CH 2 OH, R = H, R 1 = CH 3 ; f, R = CH 2 OH, R = H, R 1 = Ph [17]; g, R = R = H, R 1 = CH 2 OH [14]; h, R = R = CH 2 OH, R 1 = H; i, R = CH 2 OH, R = i-Pr, R 1 = H; j, R = CH 2 OH, R = CH 2 Ph, R 1 = H; k, R = C(CH 3 ) 2 OH, R = R 1 = H [18]). The research has also been extended to anionic closo-rhodacarboranes with the dicyclopentadiene (DCPD) ligand bound to the metal vertex [19][20][21][22][23].…”

“…These are as follows: (i) the protonation of the PPN + salts of the corresponding anionic closo-{ 4 -(C 7 H 7 -2-CR 2 OH)}rhodacarborane complexes with HPF 6 (synthesis of 111a-g), (ii) the thermal reaction in benzene between carbinols NBD-2-CR 2 OH (R = H or Me) and the Scheme 42. Synthesis of closo-( 3 , 2 -norbonadienyl)rhodacarboranes 111a-k [17,18,70,89] Using chiral stationary phase HPLC, racemic complexes 111a, b, h and 113 were successfully resolved into enantiomers and their chiroptical properties (rotation angles and CD spectra) were investigated [87]. closo-( 3 , 2 -Norbonadienyl)rhodacarboranes with mono-C-substituted carborane ligands were usually formed in the reactions as mixture of diastereomers.…”

“…In a series of papers, we have reported our results on the synthesis [17,18,70,[87][88][89][90], structural and stereochemical studies [87][88][89][90], and the application in catalysis [90][91][92][93] of closo-(-norbonadienyl)rhodacarboranes based on [7,nnido-C 2 B 9 H 11 ] 2− derivatives (n = 8 or 9). Thus, complexes of the type [ [17,70] were prepared by three different synthetic methods.…”

“…Thus, complexes of the type [ [17,70] were prepared by three different synthetic methods. These are as follows: (i) the protonation of the PPN + salts of the corresponding anionic closo-{ 4 -(C 7 H 7 -2-CR 2 OH)}rhodacarborane complexes with HPF 6 (synthesis of 111a-g), (ii) the thermal reaction in benzene between carbinols NBD-2-CR 2 OH (R = H or Me) and the Scheme 42.…”

“…Synthesis of anionic closo-( 4 -cyclodiene)rhodacarboranes 18-a-f [13][14][15], 21a-k [14,[16][17][18], and 22a-f [19][20][21]. Scheme 5.…”