Regiospecific and sequential P–C bond activation/cluster transformations in the reaction of PhCCo2MoCp(CO)8 with the diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf)

Non-innocent bma ligand in a dissymetrically disubstituted diiron dithiolate related to the active site of the [FeFe] hydrogenases

“…1). Formation of 1 could result from a well-known P-C bond cleavage in the bma ligand [28,29,32] and a formal, scarce C-H bon activation of a methyl group in Me 3 N [38,39]. To the best of our knowledge, few examples of C-H bond activation in tertiary amines were previously reported [38][39][40].…”

“…Numerous functionalities with specific electronic and steric effects could be introduced in diiron systems through these chelating groups [26,27]. In light of this, we decided to use the 2,3-bis (diphenylphosphino) maleic anhydride (bma) [28][29][30][31][32][33][34] to prepare a diiron compound holding a chelating redox-active ligand as a surrogate of the [4Fe4S] cubane. As compared to 1,2-bis(diphenylphosphino)ethane (dppe, Ph 2 PCH 2 CH 2 PPh 2 ) or 1,2-bis(diphenylphosphino)ethylene (dppv, Ph 2 PCH = CHPPh 2 ), bma exhibits a radically different electronic behavior because of a low-lying π*orbital delocalized over the maleic anhydride ring [30,31].…”

Ligand substitution in the tetrahedrane clusters RCCo2Mo(η5-indenyl)(CO)8 with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd): Influence of the carbyne and indenyl ligands on the stability of the substitution products and X-ray diffraction structures of HCCo2Mo(η5-indenyl)(CO)6(μ-bpcd) and CoMo(η5-indenyl)(μ-CPh)(CO)2(μ-bpcd)Cl

“…Our groups have been actively studying the ligand substitution chemistry of the homometallic tetrahedrane clusters RCCo 3 (CO) 9 with the redox-active diphosphine ligands 2,3-bis(diphenylphosphino)maleic anhydride (bma) and 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) for the last several years. While the substitution chemistry exhibited by the two diphosphine ligands with the RCCo 3 (CO) 9 clusters is identical, the bma-substituted derivatives tend to be more difficult to purify by column chromatography due to the supportpromoted hydrolysis of the anhydride moiety.…”

“…While the substitution chemistry exhibited by the two diphosphine ligands with the RCCo 3 (CO) 9 clusters is identical, the bma-substituted derivatives tend to be more difficult to purify by column chromatography due to the supportpromoted hydrolysis of the anhydride moiety. Accordingly, we have begun to devote a greater amount of our attention to the examination of the chemistry associated with the bpcd ligand.…”

“…Accordingly, we have begun to devote a greater amount of our attention to the examination of the chemistry associated with the bpcd ligand. These particular ligands, whose structures are depicted below, react with RCCo 3 (CO) 9 to give the corresponding diphosphinesubstituted clusters RCCo 3 (CO) 7 (P-P) [1][2][3][4][5]. The RCCo 3 (CO) 7 (P-P) clusters are of interest as they display dynamic, non-dissociative chelate-to-bridge diphosphine isomerization about the cluster polyhedron and facile cluster/diphosphine activation at ambient temperatures.…”