Synthesis and reactivity of [NBu4]+[Pt(III)(C6Cl5)4]-: molecular structures of [NBu4]2+[Pt(C6Cl5)4]2-.cntdot.2CH2Cl2, [NBu4]+[Pt(III)(C6Cl5)4]- and [NBu4]+[Pt(C6Cl5)4(NO)]-

The synthesis and chemical and spectral characterizations of compounds [ N B ~ ~ ] ~ + [ P t ( c ~(lc)l,~ ) ~ ] ~ - [NBu ~ ]+[ P ~ (C~(C21~, [~N)B~ ]u-~ ]+[P~(C~CI~)(~31N, aOn]d- [NBU~]+[P~(C~C~,)~(4() ParPe~ d~es)c]ri-be d in this paper. By far the most intriguing complex is 2, the first mononuclear Pt(II1) complex ever reported. [NBu4]+[Pt(C&l5),]-( 2) can be prepared by reacting [NBu4]2+[Pt(C,C15)4]2(-1 ) with various oxidants such as C12, Br2, 12, or T1C13 and also by the electrochemical oxidation of 1 at 0.7 V in CH2C12. Compound 2 is stable to air and moisture, shows very limited reactivity, and has magnetic properties consistent with a 1/2 spin system. Complex 2 reacts with NO gas to give the adduct [NBu4]'[Pt(C6Cl5),(NO)]- (3), which can also be made directly from 1 by reaction with [NO]+[ClO,]- under an atmosphere at NO. Attempts to make the corresponding fluorine analogue of the Pt(II1) complex [NBu4]+[Pt(C6F,),]w- ere unsuccessful. The X-ray structures of complexes 1-3 have been determined and are also reported in this aper. Complex 3 crystallizes in the tetragonal space group P4,lnbc (no. 1331, with a = b = 14.948 (6) c = 23.488 (9) 8, V = 5248 (3) %r3, and p(calcd) = 1.85 g cm-3 for 2 = 4. The structure has been refined to a final agreement factor of R = 6.6%