Tetragonal co-ordination polymers of rhodium(I) with stereochemically rigid aryl di-isocyanide linkages

Feinstein-Jaffe, Irene; Frolow, Felix; Wackerle, Lorenz; Goldman, Alexander; Efraty, A.

doi:10.1039/dt9880000469

Cited by 31 publications

(22 citation statements)

References 2 publications

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“…The positions of the hydrogen atoms on the central backbone atoms were not determined. Preliminary investigations showed that homoleptic complexes of the type fuc-[Cr (32),] 34 can be obtained by the reaction of the tripodal ligand with bisnaphthalenechromiThe bright red compound 34 was isolated in 60% yield ( Table 2).i691 Cr(o) complexes with six monodentate aliphatic isocyanide ligands have already been obtained from bisnaphthalenechromium in analogous The classic method for the synthesis of hexaisocyanidechromium(o) compounds using chromium(1r) leads with 32 to higher oligomers, whose molecular structures have so far not been elucidated. [691…”

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confidence: 99%

The Coordination Chemistry of Multidentate Isocyanide Ligands

Hahn

1993

Angew. Chem. Int. Ed. Engl.

111

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In spite of the excellent ligation properties of isocyanides, until a few years ago there was only a small number of known multidentate ligands of this type. One of the reasons for this lack of interest, when compared to monodentate isocyanides, was the linear arrangement of the M-C=N-R group, which usually inhibits the formation of mononuclear chelate complexes and leads to the formation of multinuclear or polymeric metal complexes. In these, the multidentate ligand acts in a monodentate Fdshion towards each metal atom. Only recently has a series of polyisocyanides with large ligand backbones been synthesized successfully. Bidentate isocyanides can bridge two metal atoms or react to give chelates with only one metal center. Tripodal ligands form mono-or binuclear complexes, in which the largest organometallic rings observed to date occur (up to 36 atoms). This class of ligands promises to be interesting for the synthesis of stable, diagnostically important technetium complexes of the type [Tc(CNR),]'. There also appear to be applications for tripodal isocyanides in catalysis. A facial, chiral Cr(CNR*), unit might be able to catalyze the hydrogenation or isomerization of prochiral double bonds. It is even possible to bind triisocyanides with suitable backbones to carbonyl trimetal clusters, thereby stabilizing them, or making selective cluster formation possible. Coordinated isocyanides can be transformed readily into carbene ligands, which, in the future, could lead to complexes with polycarbene ligation.

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confidence: 99%

The Coordination Chemistry of Multidentate Isocyanide Ligands

Hahn

1993

Angew. Chem. Int. Ed. Engl.

111

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“…Neutral rhodium(I) complexes such as [{Rh(CO) 2 Cl} 2 ] and [{Rh(cod)Cl} 2 ] (cod = cyclo-octa-l,5-diene) have been observed to undergo facile exchange reactions with monoisocyanides to afford cationic complexes of the type [Rh(CNR) 2 ] + , which oligomerize through weak intermetallic interactions to form the polynuclear cations [{Rh(CNR) 4 }J n+ . Therefore, anticipating similar coordination chemistry with aryl diisocyanides, the preparation of some rhodium(I) polymers with stereochemically rigid linkages was carried out by reacting [{Rh(CO) 2 Cl} 2 ] with various diisocyanides(L) (Table 1) in CH 2 C1 2 at 25 °C.…”

Section: Rhodium Polymersmentioning

confidence: 99%

“…^ [{Rh(CO) 2 Cl} 2 ] + 2nL -» [Rh(L) 2 ] n J + 2nCO f (1) A noteworthy feature of the polymers is connected with their ability to absorb water when exposed to air. Therefore, they are best formulated as [{Rh(L) 2 Cl 2 -xH 2 0}] n unless they are rigorously dried.…”

Section: Rhodium Polymersmentioning

confidence: 99%

“…The diffraction trace data of several coordination polymers of the type [Rh(L) 2 Cl] n with the linkages 4,4-di-isocyanobenzene, 1,4-di-isocyanonaphthalene, 4,4'-di-isocyanobiphenyl, 1,5-di-isocyanonaphthalene, 2,4-diisocyanotoluene, or bis(4-isocyanophenyl)methane are available in supplementary publication no. SUP56697 /2/.…”

Section: Reviews In Inorganic Chemistrymentioning

confidence: 99%

“…The reaction of [Rh(CO) 2 Cl] 2 with 4,4'-di-isocyanobiphenyl has been reported to give a two-dimensional coordination polymer of the type [Rh{(C 6 H 5 NC) 2 } + Cl"] n with stacked layers and a tetragonal structure. A second structural modification of the same empirical formula has been observed when this reaction was carried out under slightly different conditions.…”

Section: Hexagonal Modification Of [Rh{(c 6 H S Nc) 2 } + Cr] Nmentioning

confidence: 99%

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