758695-67-9Relevant academic research and scientific papers
PhP-PPh group bound to 1,8-positions of naphthalene: Preparation of cis isomer and synthesis of binuclear complex
Teramoto, Yuichi,Kubo, Kazuyuki,Mizuta, Tsutomu
, p. 3402 - 3407 (2011/10/12)
A thermodynamically less stable cis isomer of 1,2-diphosphacycle was prepared from the corresponding trans isomer. Diphosphine, in which a PhP-PPh bond bridges the 1,8-positions of naphthalene, 1,2-diphenyl-1,2- dihydronaphtho[1,8-cd][1,2]diphosphole (1), was first prepared according to a previously reported method, and the trans isomer of 1 was irradiated in tetrahydrofuran with UV-vis light to reach equilibrium with cis-1 in a trans:cis ratio of 1:2. When a similar photochemical conversion was carried out using a saturated hexane solution of trans-1, cis-1 was precipitated in a good yield of 94%. The configuration of cis-1 was confirmed by X-ray analysis. Both cis- and trans-1 diphosphine ligands were used for the preparation of binuclear gold complexes. The crystal structure of (μ-cis-1)-[AuCl]2 demonstrated that the two lone pairs of cis-1 are suitably directed for arrangement of the two gold centers in close proximity to each other. The two independent (μ-cis-1)-[AuCl]2 molecules in the crystal were found to form a dimer through the multiple intermolecular interaction among the gold centers.
Synthesis and molecular structures of dinuclear complexes with 1,2-dihydro-1,2-diphenyl-naphtho[1,8-c,d]1,2-diphosphole as a bridging ligand
Mizuta, Tsutomu,Kunikata, Satoru,Miyoshi, Katsuhiko
, p. 2624 - 2632 (2007/10/03)
A bisphosphine in which a PhP-PPh bond bridges 1,8-positions of naphthalene, 1,2-dihydro-1,2-diphenyl-naphtho[1,8-cd]-1,2-diphosphole (1), was used as a bridging ligand for the preparation of dinuclear group 6 metal complexes. Free trans-1, a more stable isomer having two phenyl groups on phosphorus centers mutually trans with respect to a naphthalene plane, was allowed to react with two equivalents of M(CO 5(thf) (M=W, Mo, Cr) at room temperature to give dinuclear complexes (OC)5M(μ-trans-1)M(CO)5 (M=W (2a), Mo (2b), Cr (2c)). The preparation of the corresponding dinuclear complexes bridged by the cis isomer of 1 was also carried out starting from the free trans-1 in the following way. Mono-nuclear complexes M(trans-1)(CO 5 (M=W (3a), Mo (3b), Cr (3c)) which had been prepared by a reaction of trans-1 with one equivalent of the corresponding M(CO 5(thf) (M=W, Mo, Cr) complex, were heated in toluene, wherein a part of the trans-3a-c was converted to their respective cis isomer M(cis-1)(CO)5. Each cis trans mixture of the mono-nuclear complexes 3a-c was treated with the corresponding M(CO)5(thf) to give a cis trans mixture of the respective dinuclear complexes 2a-c. The cis isomer of the ditungsten complex 2a was isolated, and its molecular structure was confirmed by X-ray analysis, showing a shorter W···W distance of 5.1661(3)A? than that of 5.8317(2) A? in trans-2a.
