19998-21-1Relevant articles and documents
Palladium(II) and platinum(II) complexes with bisphosphanes, [S 2C=C(CN)2]2- and [Se2C=C(CN) 2]2- as chelating ligands
Scheller, Lothar,Werner, Helmut
, p. 76 - 80 (2012/03/13)
The palladium(II) and platin(II) 1, 1-dicyanoethylene-2, 2-dithiolates [(L-L)M{S2C=C(CN)2}] (M = Pd: L-L = dppm, dppe, dcpe, dpmb; M = Pt: dppe, dcpe, dpmb) were prepared either from[(L-L)MCl2] and K2[S2C=C(CN)2] or from [(PPh 3)2M{S2C=C(CN)2}] and the bisphosphane. Moreover, [(dppe)Pt{S2C=C(CN)2}]was obtained from [(1, 5-C8H12)Pt{S2C=C(CN)2}] and dppeby ligand exchange. The 1, 1-dicyanoethylene-2, 2-diselenolates[(dppe) M{Se2C=C(CN)2}] (M = Pd, Pt) were prepared from[(dppe)MCl2] and K2[Se2C=C(CN) 2]. The oxidation potentials of the square-planar palladium and platinum complexes were determined by cyclic voltammetry. The reaction of [(dcpe)Pd(S2C=O)] with TCNE led to a ligand fragment exchange and gave the 1, 1-dicyanoethylene-2, 2-dithiolate [(dcpe)Pd{S2C=C(CN) 2}] in good yield. Copyright
Air-stable, recyclable, and regenerative phosphine sulfide palladium(0) catalysts for C-C coupling reaction
Aizawa, Sen-Ichi,Majumder, Arpi,Yokoyama, Yukihiro,Tamai, Mitsuyoshi,Maeda, Daisuke,Kitamura, Akina
, p. 6067 - 6072 (2010/01/29)
Mononuclear phosphine sulfide Pd(0) complexes and a polymer-supported triphenylphosphine sulfide Pd(0) complex were prepared as new air-stable Pd(0) catalysts for C-C coupling reactions. The phosphine sulfide Pd(0) complexes are not decomposed after compl
Bis(cyclopentadienyl)phenylphosphine as ligand precursor for assembling heteropolymetal complexes
Ricci, Antonella,Angelucci, Francesco,Chiarini, Marco,Lo Sterzo, Claudio,Masi, Dante,Giambastiani, Giuliano,Bianchini, Claudio
, p. 1617 - 1625 (2009/02/01)
The dilithium salt of bis(cyclopentadienyl)phenylphosphine has been used as a multidentate ligand to generate unprecedented heteropolymetal arrays via the bimetal precursors [MI(CO)3]2[(η5-C 5H4)P(Ph)(η5-C5H4)] (9, M = Mo; 10, M = W). The trimetal complexes MI(CO)3[(η 5-C5H4)P(Ph)(η5-C 5H4)](CO)3-MPd(PPh3)I (14, M = Mo; 15, M = W), obtained by reaction of 9 and 10 with Pd(PPh3) 4, respectively, have been found to lose PPh3 converting to the hexametal derivatives {MI(CO)3[(η5-C 5H4)P(Ph)(η5-C5H 4)](CO)3MPd}(μ-I2){PdM(CO) 3[(η5-C5H4)P(Ph) (η5-C5H4)](CO)3MI} (18, M = Mo; 19, M = W). Compound 18 also has been prepared by reaction of 9 with a PPh 3-free zerovalent palladium species such as Pd2(dba) 3; treatment of 18 with PPh3 regenerated the trimetal complex 14. The pentametal complex {MoI(CO)3[(η5- C5H4)P(Ph)(η5-C5H 4)](CO)3Mo}Pd{Mo(CO)3[(η5-C 5H4)P(Ph)(η5-C5H 4)](CO)3MoI}(22), containing a linear Mo-Pd-Mo array, has been spectroscopically observed by reacting 18 with 1,2-bis(diphenylphosphino) ethane.
Palladium-catalyzed asymmetric phosphination. Enantioselective synthesis of PAMP-BH3, ligand effects on catalysis, and direct observation of the stereochemistry of transmetalation and reductive elimination
Moncarz, Julian R.,Brunker, Tim J.,Jewett, John C.,Orchowski, Michael,Glueck, David S.,Sommer, Roger D.,Lam, Kin-Chung,Incarvito, Christopher D.,Concolino, Thomas E.,Ceccarelli, Christopher,Zakharov, Lev N.,Rheingold, Arnold L.
, p. 3205 - 3221 (2008/10/08)
The complexes Pd(diphos)(o-An)(I) (o-An = o-MeOC6H4; diphos = dppe (3), (S,S)-Chiraphos (4), (R,R)-Me-Duphos (5), (R,S) -t-Bu-Josiphos (6), (R)-Tol-Binap (7)) were prepared. Complex 6 catalyzed the coupling of PH(Me)(Ph)(BH3) (2) with o-AnI in the presence of base to yield PAMP-BH3 (P(Me)(Ph)(o-An)(BH3) (1)) in low enantiomeric excess. The course of stoichiometric reactions of 3-7 with 2 and NaOSiMe3 depended on the diphosphine ligand. Complexes 6 and 7 gave PAMP-BH3 (1) and Pd(0) species; no intermediates were observed. With 3, the intermediate Pd(dppe)(o-An)(P(Me)(Ph)(BH3)) (10) was observed by 31P NMR, while 4 gave the isolable diastereomeric palladium complexes (Sp)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11a) and (RP)-Pd((S,S)-Chiraphos)(o-An)(P(Me)(Ph)(BH3)) (11b), whose absolute configurations were determined by X-ray crystallography after separation. The analogous Pd((R,R)-Me-Duphos)(o-An)(P(Me)(Ph)(BH3)) diastereomers (12a,b) were also separated and isolated. Treatment of 4 with highly enantioenriched 2 (R or S) gave 11a or 11b in high diastereomeric excess with retention of configuration at phosphorus. P-C reductive elimination from either isomer of highly diastereoenriched 11 in the presence of excess diphenylacetylene yielded Pd((S,S)-Chiraphos)(PhC≡CPh) (14) and highly enantioenriched PAMP-BH3 (1), with retention of configuration.
Synthesis and characterization of trimetallic complexes containing M-Pd-M arrays (M = Mo, W) and their relevance in palladium-catalyzed metal-carbon bond formation
Angelucci, Francesco,Ricci, Antonella,Lo Sterzo, Claudio,Masi, Dante,Bianchini, Claudio,Bocelli, Gabriele
, p. 3001 - 3008 (2008/10/08)
The heterobimetallic complexes [MPd(PPh3)(C≡C-Ph)(CO)3(η5-C5 -C5H2Ph2(PPh2)] (5a, M = Mo; 5b, M = W) convert under chromatography to diastereomeric mixtures of the new trimetallic clusters [Pd{M(CO)3(η5-C5H2Ph2 (PPh2)}2] (M = Mo, 9a; W, 9b), which contain a linear M-Pd-M array clamped between two (diphenyl)cyclopentadienyl-diphenylphosphino ligands. Diastereomeric pure forms of both trimetallic clusters 9a,b were obtained by fractional crystallization procedures, and the molecular structures of rac-9a and rac-9b were determined by single-crystal X-ray diffraction analyses. The trimetallic complexes 9a,b have been found to be intermediates in coupling reactions between M-I moieties and Bu3Sn-C≡C-Ph, to form metallacetylides M-C≡C-Ph. Independent high-yield synthetic routes to 9a,b have been developed.
