0000000000364804
AUTHOR
Maria Angela Pellinghelli
Fast orthometalation reactions at a binuclear dirhodium(II) complex. Synthesis, crystal structure and reactivity of Rh2(O2CCH3)3[(C6H4)PPh2]·(HO2CCH3)2
Abstract From the reaction of Rh2(O2CCH3)4(MeOH)2, in hot acetic acid with PPh3 the monometalated intermediate Rh2(O2CCH3)3[(C6H4)PPh2](HO2CCH3)2 has been isolated and characterized by an X-ray study. This compound rapidly reacts with an excess of PPh3 in dichloromethane at room temperature to give Rh2(O2CCH3)2-[(C6H4)PPh2]2(PPh3)2 with a head-to-tail structure. The same procedure at higher temperatures gives a mixture of this compound and another doubly metalated compound with a head-to-head structure.
A New Conducting Molecular Solid Based on the Magnetic [Ni(dmf)6]2+ Cation and on [Ni(dsit)2]22− (dsit=1,3-dithiole-2-thione-4,5-diselenolate) Showing an Unprecedented Anion Packing
The synthesis, X-ray structure, magnetic and transport properties of the compound Ni(dmf) 6 [Ni(dsit) 2 ] 2 (dmf=dimethylformamide, dsit = 1,3-dithiole-2-thione-4,5-diselenolate) are described. This compound crystallizes in the monoclinic space group P2 1 /c, with a = 18.709(6), b = 22.975(5), c = 20.418(5) A, β = 99.31(2)° and Z = 6; its structure consists of [Ni(dsit) 2 ] 2- 2 dimers and isolated [Ni(dmf) 6 ] 2+ cations both centrosymmetric and non-centrosymmetric. The dimers are packed forming chains along the [101] direction with short Se...Se interdimer contacts. Additional interchains S...S contacts render this structure a three-dimensional character, never observed so far in other [N…