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| 1. |
A Comparison of Some Aspects of the Aqueous Coordination Chemistry of Aluminum(III) and Iron(III) |
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Comments on Inorganic Chemistry,
Volume 8,
Issue 1-2,
1988,
Page 1-26
AlvinL. Crumbliss,
J.Mark Garrison,
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摘要:
The aqueous coordination chemistry of Al3+and Fe3+is compared. The differences in electronegativities (Xm), ionic radii (ri) and electron configuration (dn) for the two ions are shown to influence trends in aquo ion structure and reactivity, hydrolysis, and metal complex stability. Similarities in coordination chemistry result in similarities in distribution and modes of transport for Al3+and Fe3+in a biological system.
ISSN:0260-3594
DOI:10.1080/02603598808048670
出版商:Taylor & Francis Group
年代:1988
数据来源: Taylor
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| 2. |
Reactions of Coordinated Ligands Exemplified by the Formation and Transformation of the Dithiocarbonate Ligand in the Rhodium(III) Complex [(triphos)Rh(S2CO)]BPh4 |
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Comments on Inorganic Chemistry,
Volume 8,
Issue 1-2,
1988,
Page 27-43
Claudio Bianchini,
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摘要:
The genesis and chemistry of the S,S-chelate dithiocarbonate ligand in the Rh(III) complex [(triphos)Rh(S2CO)]BPh4, (1), [triphos = MeC(CH2PPh2)3] have been investigated by means of a variety of chemical and physical techniques. Compound1in CH2Cl2or THF solutions thermically or photochemically decomposes affording, depending on the reaction conditions, CO and the bis(μ-S2) complex [(triphos)Rh (μ-S2)2Rh(triphos)](BPh4)2or COS and the bis(μ-S) complex [(triphos)Rh (μ-S)2Rh(triphos)](BPh4)2. The latter, which can be also obtained by treatment of1with H+or Me+, reacts with O2yielding the bis(μ-SO) derivative [(triphos)Rh(μ-SO)2Rh(triphos)](BPh4)2. Nucleophiles such as halides, pseudohalides and H−, add to rhodium to form neutral, octahedral complexes of general formula (triphos)Rh(S2CO)(Nu). Heteroallene molecules of the S˭C˭X type (X = S, O, NR) are metathesized by1to give the trithiocarbonate or dithiocarbimate derivatives [(triphos)Rh(S2CS)]BPh4and [(triphos)Rh(S2CNR)]BPh4(R = Ph, Et), which, together with1, are able to heterolytically split dihydrogen under very mild conditions. As a result, the hydride (triphos)RhH(S2CS), the hydrido(dithiocarbamate) (triphos)RhH(S2CNHR) or the μ-SH dimeric hydride [(triphos)RhH(μ-SH)2RhH(triphos)](BPh4)2are obtained, respectively. Finally,1is chemically or electrochemically reduced to the Rh(II) congener (triphos)Rh(S2CO) which represents one of the very few examples of mononuclear Rh(II) complexes stable both in the solid state and in solution.
ISSN:0260-3594
DOI:10.1080/02603598808048671
出版商:Taylor & Francis Group
年代:1988
数据来源: Taylor
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| 3. |
Redox Changes in Mononuclear Copper Complexes Containing the N2S2Donor Set. Electrochemical Parameters as a Probe of the Structural Features |
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Comments on Inorganic Chemistry,
Volume 8,
Issue 1-2,
1988,
Page 45-78
Piero Zanello,
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摘要:
The electrochemical behavior of a wide series of CuN2S2complexes is examined. The stereodynamic copper(II)/copper(I) redox change is by far the most important one in this type of derivative, which in many cases constitutes a valid model for blue copper proteins. Both the thermodynamic and kinetic aspects of the electrode processes are correlated to the stereochemical reorganizations accompanying the redox changes, as well as to the electronic effects of the ligands.
ISSN:0260-3594
DOI:10.1080/02603598808048672
出版商:Taylor & Francis Group
年代:1988
数据来源: Taylor
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