000075679 001__ 75679
000075679 005__ 20190709135621.0
000075679 0247_ $$2doi$$a10.1021/acs.organomet.7b00746
000075679 0248_ $$2sideral$$a103569
000075679 037__ $$aART-2017-103569
000075679 041__ $$aeng
000075679 100__ $$0(orcid)0000-0002-6016-0431$$aFortuño, C.$$uUniversidad de Zaragoza
000075679 245__ $$aSolvent-Driven P-S vs P-C Bond Formation from a Diplatinum(III) Complex and Sulfur-Based Anions
000075679 260__ $$c2017
000075679 5060_ $$aAccess copy available to the general public$$fUnrestricted
000075679 5203_ $$aThe outcome of the reaction of the Pt(III), Pt(III) complex [(C6F5)2PtIII(µ-PPh2)2PtIII(C6F5)2](Pt-Pt) (1) with the S-based anions thiophenoxide (PhS-), ethyl xanthogenate (EtOCS2 -), 2-mercaptopyrimidinate (pymS-), and 2-mercaptopyridinate (pyS-) was found to be dependent on the reaction solvent. The reactions carried out in acetone led to the formation of [NnBu4][(RF)2PtII(µ-PhS-PPh2)(µ-PPh2)PtII(RF)2] (2), [NnBu4][(RF)2PtII(µ-EtOCS2-PPh2)(µ-PPh2)PtII(RF)2] (3), [NnBu4][(RF)2PtII(µ-pymS-PPh2)(µ-PPh2)PtII(RF)2] (4), and [NnBu4][(RF)2PtII(µ-pyS-PPh2)(µ-PPh2)PtII(RF)2] (5), respectively (RF = C6F5). Complexes 2-5 display new Ph2P(SL) ligands exhibiting a ΰ2-P, S bridging coordination mode, which is derived from a reductive elimination of a PPh2 group and the S-based anion. Carrying out the reaction in dichloromethane afforded, in the cases of EtOCS2 - and pymS-, the monobridged complexes [NnBu4][(PPh2RF)(RF)2PtII(µ-PPh2)PtII(EtOCS2)(RF)] (6) and [NnBu4][(PPh2RF)(RF)2PtII(µ-PPh2)PtII(pymS)(RF)] (7), respectively, which are derived from reductive elimination of a PPh2 group with a pentafluorophenyl ring. The reaction of 1 with EtOCS2K in acetonitrile yielded a mixture of 3 and 6 as a consequence of the concurrence of two processes: (a) the formation of 3 by a reaction that parallels the formation of 3 by 1 plus EtOCS2K in acetone and (b) the transformation of 1 into the neutral complex [(PPh2RF)(CH3CN)(RF)PtII(µ-PPh2)PtII(RF)2(CH3CN)] (8), which, in turn, reacts with EtOCS2K to give 6. The 1 to 8 transformation was found to be fully reversible. In fact, dissolving 8 in acetone or dichloromethane afforded pure 1 after solvent evaporation or crystallization with n-hexane. The XRD structures of 2-4 and 6-8 were determined, and the behavior in solution of the new complexes is discussed.
000075679 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E21$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67461-P
000075679 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000075679 590__ $$a4.051$$b2017
000075679 591__ $$aCHEMISTRY, ORGANIC$$b11 / 57 = 0.193$$c2017$$dQ1$$eT1
000075679 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b7 / 45 = 0.156$$c2017$$dQ1$$eT1
000075679 592__ $$a1.652$$b2017
000075679 593__ $$aInorganic Chemistry$$c2017$$dQ1
000075679 593__ $$aPhysical and Theoretical Chemistry$$c2017$$dQ1
000075679 593__ $$aOrganic Chemistry$$c2017$$dQ1
000075679 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000075679 700__ $$0(orcid)0000-0002-4808-574X$$aMartín, A.$$uUniversidad de Zaragoza
000075679 700__ $$aMastrorilli, P.
000075679 700__ $$aGallo, V.
000075679 700__ $$aTodisco, S.
000075679 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000075679 773__ $$g36, 21 (2017), 4325-4337$$pOrganometallics$$tOrganometallics$$x0276-7333
000075679 8564_ $$s1046167$$uhttps://zaguan.unizar.es/record/75679/files/texto_completo.pdf$$yPostprint
000075679 8564_ $$s83686$$uhttps://zaguan.unizar.es/record/75679/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000075679 909CO $$ooai:zaguan.unizar.es:75679$$particulos$$pdriver
000075679 951__ $$a2019-07-09-12:28:03
000075679 980__ $$aARTICLE