Palladium dinitrogen complexes

Palladium, tris(dinitrogen)-synthesis, 28 Palladium(II) complexes magnetic properties, 274 spectra, 255 square planar... 

Ghedini reported a number of mononuclear cyclopalladated 2-phenylpy-rimidine complexes, some of them, 17 and 18, showing mesomorphic properties [26]. These compounds were obtained by bridge splitting reactions from the dinuclear (/ -chloropyrimidine)palladium(II) complexes with various acetylacetone and dinitrogen ligands. 

No reactions of complexes 62 and 63 have been reported. Palladium and platinum form no well-defined dinitrogen complexes. However, until relatively recently there were few carbonyl complexes of palladium and platinum. This has changed rapidly with the preparation of a wide variety of compounds such as dinuclear complexes, e.g., [M2Cl2(ju,-CO)-(ju. -dppm)2] where M = Pd, Pt, and neutral and anionic polynuclear complexes such as [Os2(CO)6 /t-Pt-(CO)(PPh3) 2] and [Pt9(CO)i8]. The absence of simple, mononuclear palladium and platinum dinitrogen complexes should not be construed as evidence that this is a barren area for research. 

On the other hand, sulphur reacts with the palladium azide complex to give a dimer which is linked by N atoms as indicated in (8.113). Unlike in the copper complex where all the N-N distances are equal, unequal distances in the palladium complex indicate the triple bonds as shown (8.97). Dinitrogen may act as a bridging group as in... 

Ozin GA, Klotzbuecher WE. Binary mixed dioxygen dinitrogen complexes of nickel, palladium, and platinum, (02)M(N2)n (where M = nickel, palladium, or platinum n=l or 2).JAm Chem Soc. 1975 97 3965-3974. 

Palladium, polymethylenebis(diphenylphosphine)-bis(thiocyanato)-linkage isomers, 1, 185 Palladium, tetraammine-tetrachloropalladate history, 1, 2 Palladium, tetrachloro-crystal structure, 1, 16 Palladium, tris(dinitrogen)-synthesis, 1,28 Palladium complexes a,(5-dione dioximates electrical properties, 6, 143 acetylacetone hydrolysis, 2,379 alkylperoxo... 

A remarkable process was reported by Mori that forms aniline from dinitrogen (Equation (26)).106 Titanium nitrogen fixation complexes were generated from reactions of titanium tetrachloride or tetraisopropoxide, lithium metal, TMS chloride, and dinitrogen. These complexes generated a mixture of aryl and diarylamines in yields as high as 80% when treated with aryl halide and a palladium catalyst containing DPPF ... 

The reaction of cycloalkeno-l,2,3-selenadiazole 183 with a mixture of [Pd2(dba)3] and trialkylphosphine in toluene under reflux for 1 h gave the novel complexes 51 in 36-55% yields (dba = dibenz[ ] anthracene) <2004POL2967, 1998CC1305>. The molecular structure of complex 51 (n = 1, R = Bu) was determined by X-ray crystallography. The proposed mechanism is shown in Scheme 18. Insertion of palladium(O) into the selenium-nitrogen bond of 1,2,3-selenadiazole occurs, followed by 1,3-dipolar addition of a selenaketocarbene 185 formed in situ by thermal elimination of dinitrogen with the elimination of a trialkylphosphine. 

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