Transfer systems, mononuclear

Mononuclear Transition Metal Charge Transfer Systems... 

In the presence of strong alkali, the rhodium analog of 62, or RhCl(C8H,2)PPh3, hydrogenates aliphatic ketones at 1 atm and 20°C, and after treatment with borohydride the systems similarly reduce aromatic ketones to the alcohols (526). Deuterium exchange data for acetone reduction were interpreted in terms of hydrogen transfer within a mononuclear hydroxy complex containing substrate bound in the enol form (63). 

Although there is a huge body of research on the kinetics of outer-sphere electron-transfer reactions of mononuclear transition-metal complexes, there are only a small number of papers on dinuclear systems. When the valences of the two metal centers are localized, current evidence indicates that the metal centers typically react essentially independently. On the other hand, for delocalized systems this can hardly be the case. Experimental study of electron transfer with such... 

By the example of 34 different alkynes, it was convincingly demonstrated that the product of the treatment of [PtCLJ with CO at 40-110 °C is a very powerful alkyne hydration catalyst some of the reactions are shown on Scheme 9.7 [25], The best medium for this transformation is THF containing 5 % H2O. The reaction can also be performed in a water-organic solvent two-phase system (e.g. with 1,2-dichloroethane), however in this case addition of a tetralkylammonium salt, such as Aliquat 336, is required to facilitate mass transfer between the phases. After the reaction with CO, the major part of platinum is present as H2[ Pt3(CO)6 n], but the catalytic effect was assigned to a putative mononuclear Pt-hydride, [PtHCl(CO)2], presumably formed from the cluster and some HCl (supplied by the reduction of [PtCU]). The hydration of terminal acetylenes follows Markovnikov s mle leading exclusively to aldehyde-free ketones. 

It is unknown what role is played by ligand environments in proteins and in synthetic analogues in stabilizing different species as it is also unknown which species represent active oxidants capable of transfering oxygen atoms to substrate in the enzyme systems. Moreover, it is not known how a binuclear metal active site might differ tom a mononuclear active site or if there is one type of reaction mechanism that operates in all or most of the monooxygenase enzymes or if each type of enzyme follows a different mechanism. 

The 02 ion appears to play an important role in a number of photooxidation reactions (see Section VI,C) for example, the photo-oxidation of alkenes over TiOz. However, it seems likely that OJ is not, in many cases, active in the oxidation step but further conversion occurs to give a mononuclear species, not detected directly, which then oxidizes the adsorbed hydrocarbons. Photo-oxidation of lattice oxygen in the M=0 systems (e.g., V2Os supported on PVG) gives rise to an excited charge transfer state such as V4 + -0 . This excited state can react as O- either by addition to a reactant molecule or by an abstraction reaction (see Section V of Ref. /). In the presence of oxygen, 03 is formed which then reacts further with organic molecules. 

Tables I and II summarize the structural studies of mononuclear and binuclear vinylidene complexes, and Table III those of propadienylidene complexes which had been reported to mid-1982. As can be seen, the C=C bond lengths range from 1.29 to 1.38 A, and the M-C bond (1.7-2.0 A) is considerably shorter than those found in alkyl or simple carbene complexes. Both observations are consistent with the theoretical picture outlined above, and in particular, the short M-C bonds confirm the efficient transfer of electron density to the n orbitals. In mononuclear complexes, the M—C=C system ranges from strictly linear to appreciably bent, e.g., 167° in MoCl[C=C(CN)2][P(OMe3)2]2(fj-C5H5) these variations have been attributed to electronic rather than steric factors. In the molybdenum complex cited, the vinylidene ligand bends towards the cyclopentadienyl ring (111).

Spontaneous transfer reactions in conjugated diene polymerisation systems are more complex than those in monoalkene polymerisation systems. Two types of chain termination reaction can occur in principle in polymerisation systems containing conjugated diene. The first type, mononuclear termination, consists in a hydrogen abstraction from the growing chain with the formation of an Mt H bond [scheme (7)] which reforms an Mt [ /3-(All)] bond on reaction with the monomer ... 

Recently, the formation of the dinuclear Eu(II) complex at the toluene-water interface was found out by a time-resolved total reflection fluorometry. When bathophenanthroline sulfate (bps) was added to the extraction system of Eu(III) with 2-thenoyltrifluoroacetone (Htta), a double component luminescence decay profile was observed and it showed the presence of dinuclear complex at the interface [27]. The observed life times x — 22 and 203 ps were attributed to the dinuclear complex Eu2(tta)2(bps)2 and the mononuclear complex Eu(tta)2bps. The shorter lifetime of the dinuclear complex than x = 98 ps for an aqua-Eu(III) ion suggested a charge transfer deactivation in the dinuclear complex. 

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