Complexes irradiation

Where X is phenyl, the result of irradiation (sunlight, mercury lamp) is the formation of Ru(NO)X3(PPh3)(OPPh3) (X = Cl, Br) in the case of the diethyl-phenylphosphine complex, irradiation causes isomerization to the cis,mer-isomer. The frans,mer-isomer is the usual synthetic product, but in the case of dimethylphenylphosphine the/ac-isomer was obtained using short reaction times it isomerized to the usual mer,trans-isomer on heating [123],... 

Host-guest complex Irradiation time (h) Product ... 

Complex Irradiating wavelength, m/i Reaction mode Quantum yield4 Refs. 

Complex Irradiating wavelength, mil Reaction mode Quantum yieldd Refs. 

Coordinated azide ion will undergo a number of reactions which involve attack at the azide ligand. A number of examples are summarized in Scheme 9.1172-1175 The azide ligand is photochemically dissociated from bis azide complexes. Irradiation of Pt(CN)4(N3) gives Pt(CN)4 and the azide radical (equation 366),1176 whereas with Pt(N3)2(PPh3)2 the nitrogen-containing product is believed to be N6 (equation 367).1177... 

Complexes between tetranitromethane (which is a powerful electron acceptor) and different electron donors (aromatic substrates, alkenes, amines, sulphides, ethers) may be observed and isolated as moderately stable coloured complexes (if stored in the dark). These complexes are usually classified as CT complexes. Irradiation of complexes between alkenes and trinitromethane forms interesting products, which are derived from the nucleophilic attack of the trinitromethide. 

The ability of Sn(IV) organometallic compounds to act as both electron donors or acceptors has resulted in their use in photochromic systems38. Addition of 2-aminomethylpyridine to a solution of Sn(n-Bu) X4 (X = CH3COO, Cl or F) results in the formation of a deeply coloured solution, possibly the result of complex formation or, more likely, the formation of a charge-transfer complex. Irradiation of the solution efficiently bleaches the colour, which then recovers upon heating. 

The photo-reactivity of Fe(III) carboxylates has long been recognized and photo-decarboxylation24 and deamination25 of amino acid complexes have been known for some time. Ferrioxylate is the best known photo-active example of a Fe(III) polycarboxylate complex. Irradiation of ferrioxalate in acidic solution generates Fe(II) and C02 (Figure 5.4). 

The photochemistry of these aryl complexes has been briefly investigated by Nesmeyanov and co-workers (98,98a) and is quite similar to that of the analogous alkyl complexes. Irradiation of CpFe(CO)2Ar complexes in the presence of tertiary phosphines at room temperature led to the formation of the corresponding monosubstituted derivatives (98) [Eq. (96)]. Prolonged irradiation in the presence of triphenylphosphite... 

Irradiation of 118 in deoxygenated benzene solution gave an insoluble cobalt(II) complex which was not further characterized. Irradiation in the presence of O2 gave a clean photoreaction to yield an organometallic complex tentatively formulated as an alkylperoxo complex. Irradiation of dimethylcobalt complexes such as [(CH3)2Co(bipy)2]" (bipy = bipyridyl) 130) and (CH3)2Co(bdml,3pn) [bdml,3pn = bis-l,3-(diacetylmono-... 

The data are unambiguous. Regardless of which isomer of an isomeric pair is irradiated, the product distributions are identical within experimental error. Such results clearly suggest that the mechanism outlined in Scheme I is an accurate description of the processes occurring during irradiation of the disilane complexes. Irradiation of FpSi(CH3)2Si(CH3)2Si(CH3)3 yields not only the ultimate product FpSi(CH3)3 but also transient yields of FpSi(CH3)2Si(CH3)2. 

HMn(CO)s has been photolysed in Ar and CH4 matrices and this produces CO and HMn(CO)4, a compound having a C, structure. Narrow band photolysis also leads to small amounts of a second isomer of HMn(CO)4 which has a C4 structure. PhMn(CO)5 has been observed to photoreact with 6,6-dimethyl- and 6,6-diphenylfulvene to give Ph(CO)4Mn(T -fulvene) complexes. Irradiation of RMn(CO)jL2 [10 R = H or Me, L = P(OPh)j] and of MeMn(CO>4L in benzene induces formation of the orthometallated products (11). These arise by formation of a 16-electron intermediate which in-tramolecularly activates a C-H bond of Ph in PCOPha). ... 

With greater analytical power has come the ability to recognize and, increasingly, to characterize more complex irradiation histories. As it turns out, many meteorites retain the effects not only of recent irradiation but also of irradiations that took place at earlier times, in different settings. 

Recent work by Stone provides additional examples of the photoreactivity of carbyne carbonylmetal complexes. Irradiation of the 2,6-xylylcar-byne molybdenum complex 209 in the presence of triphenylphosphine affords the ketenyl complexes 210, which slowly transform into the tri-phenylphosphine-substituted carbyne complexes 211 [Eq. (165)] (J5). In... 

POM acceptor complexes irradiation of EDA band shows at least two distinct species formed in <80 ps... 

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