742078-08-6Relevant articles and documents
Thiocarbarmoyl-assisted formation of a new type of α-and β-isomer paddlewheel Pd24+ compounds. Synthesis, characterization, and crystal structures of [Pd(η1-SCNMe 2)(η2-Tp)(PPh3)]
Yih, Kuang-Hway,Lee, Gene-Hsiang
, p. 3397 - 3403 (2010/09/17)
The reaction of the doubly thiocarbamoyl-bridged boat-form complex [Pd(PPh3)(Cl)]2(μ-SCNMe2)2, 1, with dithio (SS) and tris(pyrazoyl-1-yl)borate (Tp) ligands produces the monomer η1-thiocarbamoyl complexes [Pd(PPh3) (η1-CSNMe2)(η2-SS)] (SS = Et 2NCS2, 2a; (EtO)2PS2, 2b) and [Pd(PPh3)(η1-CSNMe2)(η2-Tp)] , 3, respectively. Treatment of 1 with dialkyldithiocarbonate, ROCS 2-, yields Fischer-type carbene complexes [Pd(PPh 3){η1-C(SR)(NMe2)}(η2-S 2CO)] (R = Me, 4a; Et, 4b). The carbene complexes 4a and 4b are formed via alkyl migration of the alkyldithiocarbonate ligand to the thiocarbamoyl ligand. The organometallic α-isomer paddlewheel-type Pd 24+ dipalladium complex without axial ligation, [Pd 2(μ-Hdppa)2(μ-SCNMe2)2][Cl] 2, 5, is prepared by the reaction of Hdppa (Hdppa = bis(diphenylphosphino)amine) with 1. Treatment of 5 with anionic oxygen, nitrogen, or carbon reagents (KOH, NaN3, NaNH2, NaCCH), instead of forming axial ligation complex, yields the deprotonation of the Hdppa ligand of 5 to obtain the α-isomer paddlewheel Pd2 4+ complex [Pd2(μ-dppa)2(μ-SCNMe 2)2], 6. Protonation of 6 by HBF4 or HCl gave 5 quantitatively as the BF4- and Cl- salts, respectively. In the reaction of 5 with KTp, instead of forming a Tp-Pd complex, complex 6 was formed. The β-isomer paddlewheel complexes containing a Pd24+ core, [Pd(η2-dithio)] 2(μ-dppa)(μ-SCNMe2) (dithio = S2P(OEt) 2, 7a; S2COEt, 7b; S2CNC4H 8, 7c), are prepared by reactions of 5 with various dithio ligands, [NH4][S2P(OEt)2], [K][S2COEt], and [NH4][S2CNC4H8], in methanol at ambient temperature, respectively. X-ray structures of the new type of α-and β-paddlewheel Pd24+ species have been determined.
