Paramagnetic Platinum–Rhodium Octamers Bridged by Halogen Ions To Afford a Quasi‐1D System

Uemura, Kazuhiro; Fukui, Kôichi; Nishikawa, Hiroyuki; Arai, Saiko; Matsumoto, Kazuko; Oshio, Hiroki

doi:10.1002/anie.200501049

Cited by 61 publications

(24 citation statements)

References 46 publications

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“…A substantial number of platinum(III)-involved oligo-nuclear complexes having Pt(III)-Pt(III)/(II) or Pt(III)-other-metal bonds has been widely investigated to date because their metal-metal interactions are expected to induce novel chemical and/or physical properties, e.g., effective and selective catalysts for organic reactions [1][2][3], and creation of functional metal-1D chain compounds [4][5][6][7][8], etc.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

Iwatsuki

Ishihara

Matsumoto

2006

Science and Technology of Advanced Materials

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The axial water ligand substitution reaction on the head-to-head (HH) and head-to-tail (HT) amidato-bridged cis-diammineplatinum(III) binuclear complexes, HH-and HT-[Pt 2 (NH 3 ) 4 (m-amidato) 2 (OH 2 ) 2 ] 4+ (amidato ¼ a-pyridonato, a-pyrrolidonato, or pivalamidato), with halide ions (X À ¼ Cl À , Br À ) in acidic aqueous solution reveals a consecutive 2-step kinetics under the pseudo first-order conditions of a large excess concentration of halide ion relative to that of the complex ðC X À bC Pt Þ, corresponding to formation of the monohalo (step 1) and the dihalo complexes (step 2). The first substitution step of all the HH and HT diaqua dimers consists of two parallel reaction pathways: one is the simple substituion path of one of the coordinated aqua ligands with X À , and the other is the replacement in the aquahydroxo complex which is the conjugate base of the diaqua dimer. In step 2, there are three reaction pathway patterns: the direct substitution path, the path via a coordinatively unsaturated intermediate, and the unusual path of OH À replacement.Step 2 proceeds via either one or two paths of the three depending on the nature of the halide ion as well as the bridging ligand. On the other hand, the substitution reaction of the hydrogenphosphato-bridged lantern-type complex, [Pt 2 (m-HPO 4 ) 4 (OH 2 ) 2 ] 2À proceeds in 1-step at C X À bC Pt , in which the first aqua ligand substitution to form the monohalo species is rate-determining and the monohalo species is in rapid equilibrium with the dihalo complex. The rate-determining step consists of parallel pathways similar to step 1 in the amidato-bridged complex systems. r

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Section: Introductionmentioning

confidence: 99%

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

Iwatsuki

Ishihara

Matsumoto

2006

Science and Technology of Advanced Materials

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“…As shown in Table 4, the Pt-Rh distances in 1 and 2 are slightly shorter than that of Pt(+3, d 7 )···Rh(+2.5, d 6.5 ) in HMM-1. [16] In addition, the Pt-Rh distances in 1 and 2 are about 0.5 Å shorter than those reported in other Pt-Rh dinuclear complexes, trans-Rh-(CO)Cl(µ-Ph 2 AsCH 2 PPh 2 ) 2 -cis-PtC1 2 (a) [17] and [(NC) 2 PtRh(CNtBu) 2 (µ-dpm) 2 ](PF 6 ) (b, µ-dpm = bis(dipheny1phosphanyl)methane), [18] where the formal oxidation states are Pt(+2, …”

Section: Determination Of the Oxidation Statesmentioning

confidence: 97%

“…[13] As shown in Table 3, compounds 3-6 have binding energies similar to those of 1 and 2. [16] Compound 1 corresponds to a fragment of the octanuclear repetition unit in HMM-1. Because the HOMO is in the Pt-Rh dinuclear metal orbital part in HMM-1, [16] comparison between 1 and HMM-1 is meaningful.…”

Section: Determination Of the Oxidation Statesmentioning

confidence: 99%

“…[16] Compound 1 corresponds to a fragment of the octanuclear repetition unit in HMM-1. Because the HOMO is in the Pt-Rh dinuclear metal orbital part in HMM-1, [16] comparison between 1 and HMM-1 is meaningful. As shown in Table 4, the Pt-Rh distances in 1 and 2 are slightly shorter than that of Pt(+3, d 7 )···Rh(+2.5, d 6.5 ) in HMM-1.…”

Section: Determination Of the Oxidation Statesmentioning

confidence: 99%

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Synthesis, Crystal Structures, and Oxidation States of MM′X‐Type Platinum–Rhodium Dinuclear Complexes Having Amidate Bridging Ligands

et al. 2007

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Six novel Pt–Rh dinuclear complexes (1–6), [PtRh(PVM)2(NH3)2Cl3]·4H2O (1, PVM = tBuCONH–), [PtRh(PVM)2(en)Cl3]·3H2O (2, en = ethylenediamine), [PtRh(PVM)2(NH2CH3)2Cl3]·3H2O (3), [PtRh(PVM)2(NH2tBu)2Cl3]·3H2O (4), [PtRh(TCM)2(NH3)2Cl3] (5, TCM = Cl3CCONH–), and [PtRh(BZM)2(NH3)2Cl3]·H2O (6, BZM = PhCONH–), have been synthesized from Pt mononuclear complexes having nitrogen‐coordinated amidate ligands with noncoordinated amidate oxygen atoms. X‐ray analysis revealed that compounds 1 and 2 form zigzag one‐dimensional chains in the form [–Pt–Rh–Cl–]n. The oxidation states of the metal ions have been determined by X‐ray photoelectron spectroscopy (XPS) and 195Pt NMR spectroscopic analysis, and are Pt(+2, d8)···Rh(+3, d6). In comparison with the Pt–Rh distances found in the literature, it has become apparent that the Pt–Rh dinuclear complexes have a dative Pt(d8)→Rh(d6) bond, where the Pt d orbital is stabilized by the overlap with the d orbital of the Rh atom. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…Complex 1 can easily bind a second metal ion (platinum/hetero-metals) with the non-coordinated oxygen atoms in the amidate moieties, affording various dinuclear and trinuclear Pt complexes [16,17]. Furthermore, we succeeded in obtaining a novel 1-D chain from the reaction of Pt-Pt and Pt-Rh dinuclear complexes (Scheme 1) [18]. We review here the structures and unique magnetic properties of the 1-D chain complex.…”

Section: Introductionmentioning

confidence: 99%

A paramagnetic quasi-1D chain comprised of Pt/Rh possessing an unpaired electron

Uemura

Fukui

Yamasaki

et al. 2006

Science and Technology of Advanced Materials

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In this manuscript we review the structure of the novel 1-D chain complex, {[PtRh(PVM) 2 (NH 3 ) 2 Cl 2.5 ] 2 [Pt 2 (PVM) 2 (NH 3 ) 4 ] 2 (PF 6 ) 6 Á 2MeOH Á 2H 2 O} n (4) (PVM ¼ pivalamidate), consisting of mixed-valence dimeric complexes with appreciably extended metal-metal bondings. Compound 4 is made up of octameric segments, each of which consists of two platinum-rhodium dinuclear complexes and a tetrameric platinum unit. The charge of 19+ for the Pt 6 Rh 2 octameric segment in 4 was deduced from the number of the independent PF 6 À counter ions, and is the supporting evidence for one unpaired electron per one octameric segment. The tetrameric platinum unit in 4 is the structural motif that is observed in [Pt 2 (PVM) 2 (NH 3 ) 4 ](PF 6 ) 2 Á H 2 O (2) and [Pt 4 (PVM) 4 (NH 3 ) 8 ](PF 6 ) 4 (ClO 4 ) Á 2H 2 O (3 ¼ ''platinum blue'' with one electron delocalized over the four platinum atoms). On the basis of the EPR, magnetic susceptibility, and electrical conductivity results, the nature of the unpaired electron in 4 is discussed. r

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Paramagnetic Platinum–Rhodium Octamers Bridged by Halogen Ions To Afford a Quasi‐1D System

Cited by 61 publications

References 46 publications

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

Kinetics and mechanisms of the axial ligand substitution reactions of platinum(III) binuclear complexes with halide ions

Synthesis, Crystal Structures, and Oxidation States of MM′X‐Type Platinum–Rhodium Dinuclear Complexes Having Amidate Bridging Ligands

A paramagnetic quasi-1D chain comprised of Pt/Rh possessing an unpaired electron

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