Complexes heterodinuclear

The macrocychc hexaimine stmcture of Figure 19a forms a homodinuclear cryptate with Cu(I) (122), whereas crown ether boron receptors (Fig. 19b) have been appHed for the simultaneous and selective recognition of complementary cation—anion species such as potassium and fluoride (123) or ammonium and alkoxide ions (124) to yield a heterodinuclear complex (120). 

Complex 105 enters the pyrazoleAriphenylphosphine ligand substitution reaction with PPha to give 108 (910M3123). Further reaction with triphenylphosphine and silver tetrafluoroborate gives the heterodinuclear complex 109 (94IC2196). 

Usui, Y, Hrrano, M., Fukuoka, A. and Komiya, S. (1997) Hydrogen abstraction from transition metal hydrides by gold alkoxides giving gold-containing heterodinuclear complexes. Chemistry Letters, 26, 981. 

Cp(PMe3)2RuC=CH and the corresponding vinyl compound react with 1 to give the expected hydrozirconated complexes [225, 226]. Hydrozirconation reactions were also observed with the vinyl and acetylenic ferrocenyl complexes [227]. In marked contrast, the iron complex Cp (dppe)Fe-C=CH reacts anomalously with Schwartz s reagent to form acetylide Cj-bridged heterodinuclear complexes (Scheme 8-31) [228]. 

However, reaction of (2,6-xylyl)isonitrile with [Fe(CO)3( 0.-dppm) Si(OMe)3 PtH(PPh3)] led to [Fe(CO)3(it-dppm) p-CN-2,6-xylyl Pt(PPli3)] (8), a rare example of a heterodinuclear complex with a... 

Muetterties has suggested that the dimeric hydride [RhH(P OiPr 3)2]2 catalyzes alkene and alkyne hydrogenation via dinuclear intermediates [91]. However, no kinetic evidence has been reported to prove the integrity of the catalysts during the reactions. On the other hand, studies of the kinetics of the hydrogenation of cyclohexene catalyzed by the heterodinuclear complexes [H(CO) (PPh3)2Ru((u-bim)M(diene)] (M = Rh, Ir bim=2,2 -biimidazolate) suggested that the full catalytic cycle involves dinuclear intermediates [92]. 

The hydrosilylation of ethylene by the early-late transition-metal heterodinuclear complexes [CpTa( t-CH2)2lr(CO)2] has been studied mainly in a bid to recognize the mechanism of reaction, which occurs via a predominant alkene/Ir—H insertion pathway over a minor insertion of ethylene into the Ir—Si bonds [21]. 

Heterocyclic astatides, 31 74-77 Heterocyclic ligands, osmium, 37 244 Heterocysts, 38 228-230 Heterodinuclear complexes, quadruply bridged, 40 214-218... 

The thiocyanate ligands in the mercury complexes are either terminal S or 1,3-// bridge bonded. An example containing both bonding modes is Hg(NCS)2(PCy3).335 Heterodinuclear complexes have been discussed in section (vi) above. 

The bis-prolinol-derived phenol (156) has been designed to facilitate the formation of heterodinuclear complexes based upon the large difference in pKH of the phenolic OH group and the tertiary OH groups. The first examples of its application involve hydroxyacetophenones (157) as donors in the asymmetric Michael addition to nitroalkene acceptors (158) the best stereocontrol was observed with a zinc- magnesium dinuclear complex, where enantiomeric excesses ranged up to 92% for the major anti diastereoisomer (159).212... 

Alkylidyne complex [W(=CC6H4Me-4)(CO)2(bpy)Br] reacts with [Au(C6F5) (THT)] or [AuCl(THT)] to yield the heterodinuclear complexes with a tungsten -gold bond, 66 (X = C6F5, Cl) (88JCS(D)1957). 

W(CO)2(bpy)(=CC=CSiMe3)F] with tetra-M-butylammonium fluoride followed by [RuHCl(CO)(HPz )(PPh3)2] gives the heterodinuclear complex 68 (04AGE476). 

Cationic heterodinuclear complexes derived from ferrocenyl are not as common as their neutral analogs, and only the pentafluorophenyl derivative [(C6F5)Au (PPh2CH2PPh2CH2Fc)]TfO has recently been prepared by treatment of the phosphonium-phosphine salt [FcCH2PPh2CH2PPh2]TfO with equimolecular amounts of [Au(C[Pg.101]

Gunter and coworkers have synthesized a lateral macrobicyclic molecule 197 where a phorphyrin ring is capped by a bridging unit which contains a pyridino subunit. This model system for cytochrome c oxidase is in fact a heterodinuclear complex with iron(III) complexed to the porphyrin unit and copper(II) complexed to the lateral pyridino bridge. A series of these complexes have been made with... 

Heterobimetallic Complexes. Monohalide TiIV compounds containing amido,47 alkoxides,48 or tripodal amido49 groups react with many metal carbonyl cationic species to give unsupported heterodinuclear complexes such as 17-A-V. 

The ESR spectrum of the Cu —Zn heterodinuclear complex gave the well-defined ESR parameters (gy = 2.10, gJ. = 2.24,14 l = 117 G, and IA LI = 124 G), which indicate that the Cu(ll) ion in the complex has a trigonal-bipyramidal environment and a ground state (154). The observation of well-defined ESR spectmm also confirms that the complex retains its imidazolate-bridged Cu —Zn heterodinuclear structure and that it is not a 1 1 mixture of Cu —Cu and Zn Zn homodinuclear complexes. 

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