328056-67-3Relevant academic research and scientific papers
New types of group 4 and 13 metal complexes stabilized by homo- or hetero-donor functionalized dicarbollide ligands: Syntheses, characterizations, and structural studies of [{η5-C2B9H 9(D)}(η1-NMe2CH2)]M(NMe 2)2 (D = CH2NMe2, PPh2; M = Ti, Zr)
Lee, Jong-Dae,Kim, Ha-Yeon,Han, Won-Sik,Kang, Sang Ook
, p. 2348 - 2356 (2010)
A series of group 4 and 13 metal complexes coordinated to either a homo- or hetero-donor and a dicarbollyl ligand derived from N,N′- or P,N-chelated ligands were synthesized and characterized. Two homo- and hetero-donor tethered ligands of the type 7,8-(Me2NCH2)(μ-H)(Me 2NCH2)-7,8-C2B9H10 (DcabNNH, 3) and 7-PPh2-8-Me2NHCH 2-7,8-C2B9H10 (DcabPNH, 6) were prepared using the standard deborination methods from 1,2-(NMe 2CH2)2-1,2-C2B10H 10 (2) and 1-PPh2-2-Me2NCH2-1,2- C2B10H10 (5), respectively. Subsequent reactions of 3 with M(NMe2)4 (M = Ti, Zr) produced single nitrogen donors involving φ,δ-dicarbollides of the type [{- 5-C2B9H9(CH2NMe 2)}(-1-NMe2CH2)]M(NMe 2)2 (M = Ti (4), Zr (5)). Structurally similar nitrogen donor stabilized φ,δ-dicarbollides of the type [{-5-C 2B9H9(PPh2)}(-1-NMe 2CH2)]M(NMe2)2 (M = Ti (7), Zr (8)) were produced from the reaction of 6 with M(NMe2)4 (M = Ti, Zr). When group 13 metals were attempted with dissimilar ligands, 3 and 6, δ,δ-type complexes were formed with the engagement of two tethered donors at the dicarbollide ligand in an exo-polyhedral manner irrespective of the dissimilar donor properties, nitrogen or phosphine. As a result, a series of group 13 metal complexes bearing ligands 3 and 6, [(-1-NMe 2CH2)2C2B9H 10]MMe2 (M = Al (11), Ga (12)) and [(-1- PPh2)(-1-NMe2CH2)C2B 9H10]MMe2 (M = Al (13), Ga (14)), were prepared by reacting 3 and 6 with trimethylaluminum (TMA) and trimethylgallium (TMG), respectively. New types of φ,δ- and δ,δ-coordination were established by extensive structural studies of each metal complex comprising N,N′- or P,N-chelated dicarbollide: 7, 9, 10, 11, 13, and 14.
New Group 9 metal complexes containing N,P-chelate ligand system.: Synthesis, characterization and application to catalytic hydrogenation
Lee, Heung-Sae,Bae, Jin-Young,Ko, Jaejung,Kang, Yong Soo,Kim, Hoon Sik,Kim, Sung-Joon,Chung, Jang-Hoon,Kang, Sang Ook
, p. 83 - 91 (2007/10/03)
New N,P-chelating o-carboranylaminophosphine ligand CabN,P 2 [CabN,P=o-C2B10H10(CH 2NMe2)(PPh2)-N,P] was prepared from o-carboranylamine LiCabN [CabN=o-C2B10H10(CH 2NMe2)-N] and chlorodiphenylphosphine. Consequently, the reaction of [M(cod)(solv)2]+BF4- (M=Rh, Ir; cod=cycloocta-1,5-diene) with 2 was investigated. The resulting rhodium and iridium metal complexes [(CabN,P)M(cod)]+BF4- 3 (M=Rh 3a, Ir 3b) were characterized by NMR spectroscopy and elemental analysis. In addition, an X-ray structure analysis was performed on complex 3a, where the potential N,P-chelate ligand 2 was found to coordinate in a bidentate mode. The subsequent reaction of 3 with PPh3 and CO resulted in the dissociation of the N,P-chelate ligand 2 to yield the penta-coordinate metal complexes [(PPh3)2M(CO)3]+BF4 - 4 (M=Rh 4a, Ir 4b). The structure of 4a was determined by X-ray diffraction analysis, exhibiting a trigonal bipyramidal configuration with the triphenylphosphine ligands occupying axial positions. The activities of complex 3 as a catalyst precursor during the hydrogenation of cyclohexene were tested and produced the cyclohexane with 100% conversion in the case of 3a.
