The reaction between [Pd(C6H3NNR-2, X-5)Cl]2 and phosphines gives [Pd(C6H3NNTo-2,Me-5)Cl(L)] [To = C6H4Me-4, L = PEt3 (1a), PPh2Me (1b)] or trans-[Pd(C6H3N2To-2,Me-5)ClL2] (L = PEt3 (2a), PPh2Me (2b), L2 = bis(diphenylphosphino)methane = dppm (2c)) or trans-[Pd(C6H3N2X-2, R-5)Cl(μ-dppm)]2 (X = Me, R = To (3a); X = H, R = Ph (3b)), depending on the molar ratio of the reagents. Tl(OTf) (OTf = O3SCF3), AgClO4, or AgSbF6 react with 1a,b, 2a, 2c, or 3a to give, variously, [Pd(C6H3NNTo-2,Me-5)(Y)(L)] (L = PEt3, Y = TfO (4a); L = PPh2Me, Y = TfO (4b), ClO4 (4b‘)), trans-[Pd(C6H3N2To-2,Me-5)(OTf)(PEt3)2] (5), [Pd(C6H3N2To-2,Me-5)(η1-dppm)(η2-dppm)]TfO (6), or [Pd(C6H3NNR-2,X-5)(η2-dppm)]Y (X = Me, R = To, Y = TfO (7a)). Complexes [Pd(C6H3NNR-2,X-5)(η2-dppm)]SbF6 (X = Me, R = To (7a‘); X = H, R = Ph (7b)) can be prepared by reacting [Pd(C6H3NNR-2,X-5)Cl]2 with AgSbF6 and dppm. Complex 4b‘ reacts with PPh2Me to give [Pd(C6H3N2To-2,Me-5)(PPh2Me)3]ClO4 (8). Attempts to obtain single crystals of 4a, [Pd(C6H3NNR-2,X-5)(PPh3)(Me2CO)]ClO4, or 7b lead to different products. From 4, an insertion into the Pd−OTf bond of one molecule of water gives [Pd(C6H3NNTo-2,Me-5(OH2···OTf)(PEt3)] (9) while substitution of the acetone molecule by two water molecules occurs in the second case to give [Pd(C6H3NNTo-2,Me-5){(μ3-OH2)(···OClO3)(···OH2)}(PPh3)] (10). Finally, ready oxidation in the air of 7b gives [Pd(C6H4NNPh-2)(η2-dppmO)]SbF6 (11) [dppmO = bis(diphenylphosphino)methane monoxide]. [Pt(PPh3)3] reacts with [Hg(C6H3N2To-2, Me-5)Cl] to give trans-[Pt(C6H3N2To-2,Me-5)Cl(PPh3)2] (12), which in turn reacts with Tl(OTf) to give [Pt(C6H3NNTo-2,Me-5)(PPh3)2]TfO (13). Crystal structures of 2c· 1 / 2 CH 2 Cl 2 , 4b‘, 5, 6, 7a, 9, 10, and 11·2MeOH have been determined.

The ortho-metalated complex (S,S)-[Pd2{κ2(C,N)-C6H4CH2CH(CO2Me)NH2-2}2(μ-Br)2] (1b) can be prepared by refluxing in acetonitrile equimolecular amounts of Pd(OAc)2 and l-phenylalanine methyl ester hydrochloride, followed by addition of an excess of NaBr. Complex 1b reacts with 4-picoline to give the mononuclear derivative (S)-[Pd{κ2(C,N)-C6H4CH2CH(CO2Me)NH2-2}2Br(NC5H4Me-4)] (2), whose crystal structure has been determined by X-ray diffraction. The precursor of 1b, (S,S)-[Pd2{κ2(C,N)-C6H4CH2CH(CO2Me)NH2-2}2(μ-Cl)2] (1a), could not be isolated in a pure form, but it can be used as the starting material for the synthesis of functionalized derivatives of the phenylalanine methyl ester. Thus, CO and RNC (R = Xy, t Bu) insert into the Pd−C bond of 1a to afford, after depalladation, (S)-1-oxo-3-(methoxycarbonyl)-1,2,3,4-tetrahydroisoquinoline (3) and (S)-1-R-3-(methoxycarbonyl)-3,4-dihydroisoquinolinium triflate (R = tBu (4), Xy (5)), respectively. Reaction of complex 1b with bromine or iodine affords trans-(S,S)-[PdBr2{NH2CH(CO2Me)CH2C6H4-X-2}2] (X = Br (6), I (7)), which further reacts with 1,10-phenanthroline (phen) to give [PdBr2(phen)] and (S)-2-X-phenylalanine methyl ester (X = Br (8), I (9)).

Tris-cyclometalated Pt(IV) complexes are reported for the first time. The facial isomers exhibit long-lived 3LC emissions with quantum yields up to 0.49, the highest ever found for Pt(IV) complexes, combined with a strong oxidizing character in the excited state.

AuCl(SMe 2 )] reacts with HCtCR (R ) bpyl ) 2,2′-bipyridine-5-yl (1), phtpyl ) phenyl-4-(2,2′: 6′,2′′-terpyridine-4-yl) (2)) and NEt 3 (1:1:3) to afford the polymers [Au(CtCR)] n (R ) bpyl (3), phtpyl (4)). The new alkyne HCtCphccbpyl (5, phccbpyl ) 4-C 6 H 4 CtCbpyl) has been prepared by Sonogashira coupling of 4-Me 3 SiCtCC 6 H 4 I and 1 followed by desilylation of the resulting alkyne 4-Me 3 SiCtCphccbpyl. The alkynyl Au(I) complexes [Au(CtCR)L] (R ) bpyl, L ) PPh 3 (6), PTol 3 (7, Tol ) 4-MeC 6 H 4 ), PEt 3 (8); R ) phtpyl, L ) XyNC ( 9), PPh 3 (10); R ) phccbpyl, L ) PPh 3 ( 11)) have been prepared by reacting: (1) 3 or 4 with L or (2) the corresponding alkyne 1, 2, or 5 with [Au(acac)(PPh 3 )] (acac ) acetylacetonato). The reaction of 3 or 4 with diphosphines gives [{Au(CtCR)} 2 (µ-Ph 2 P(CH 2 ) x PPh 2 )] (R ) bpyl, x ) 1 (12), 2 (13), 4 (14), 10 (15); R ) phtpyl, x ) 10 ( 16)). ESI mass spectrometric studies show that complexes 12-14 are in equilibrium with the salts [Au 3 (CtCbpyl) 2 (µ-Ph 2 P(CH 2 ) x PPh 2 ) 2 ][Au(CtCbpyl) 2 ], although only when x ) 1 ( 17) was a significant concentration of the salt detected by NMR spectroscopy and isolated. The anionic complexes PPN[Au(CtCR) 2 ] (R ) bpyl ( 18), phtpyl ( 19), or phccbpyl ( 20)) have been prepared by reaction of the corresponding alkynes with PPN[Au(acac) 2 ]. Complexes 6, 10, 13, 14, 17, and 18 have been characterized by single-crystal X-ray diffraction studies. The alkynyl complexes are luminescent at room temperature, displaying dual emissions.