Metal-metal bonding in dirhodium tetracarboxylates. Trans influence and dependence of the rhodium-rhodium bond distance upon the nature of the axial ligands

Christoph, Gary G.; Koh, Y. B.

doi:10.1021/ja00500a011

Cited by 89 publications

(43 citation statements)

References 6 publications

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“…If the differences in the Rh-O distances and internal geometric parameters of carboxyl groups (the C-O bond lengths and OCO bond angles) are considered unessential, then, in the first approximation, the values of r and sin(θ/2) are expected to show a linear dependence. Data available in the literature [27][28][29][30][31][32][33][34] confirm this expectation (Fig. 2).…”

Section: Molecular and Crystal Structure Of [Rh(m-hcoo)(co) 2 ] 2 (I)supporting

confidence: 77%

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

et al. 2005

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Dirhodium(I) di( µ -carboxylato) tetracarbonyls[ Rh ( µ -RCOO )( CO ) 2 ] 2 were obtained for the first time by reacting rhodium(I) carbonyl chloride dimer [ Rh ( µ -Cl )( CO ) 2 ] 2 with silver carboxylates [1]. The authors [1] synthesized and characterized acetate, trifluoroacetate, p -fluorobenzoate, and phthalate complexes of this type and some bis(phosphine) derivatives, such as transRh ( RCOO )( PPh 3 ) 2 ( CO ) . Later, some other methods were developed for synthesizing [ Rh ( µ -RCOO )( CO ) 2 ] 2 complexes with R = CH 3 ( II ), CF 3 ( III ) [2-4] and their monocarbonyl triphenylphosphine derivatives transRh ( RCOO )( PPh 3 ) 2 ( CO ) [2,[5][6][7][8][9][10][11][12]. The authors of [4] reported the results of X-ray diffraction study of [ Rh ( µ -The structure of transRh ( CF 3 COO )( PPh 3 ) 2 ( CO ) was previously determined in [13].Rhodium(I) formate complexes became available considerably later. Thus, the carbonyl formate dimer [ Rh ( µ -HCOO )( CO ) 2 ] 2 ( I ) was synthesized for the first time via a reaction of dirhodium(II) tetraacetate with carbon monoxide in formic acid [14]. Some other methods of synthesis of this compound were reported later on in [15,16]. A series of bis(phosphine) complexes trans -Rh ( HCOO )( PR 3 ) 2 ( CO ) was also synthesized [17][18][19]. The molecular structure of transRh ( HCOO )( PPh 3 ) 2 ( CO ) ( IV ) was determined by X-ray diffraction method [17]. It should be noted that in subsequent years, rhodium(I) formate complexes with carbonyl and some other π -acceptor ligands (olefins, phosphines) were studied more intensively than other carboxylate derivatives. This is quite natural, since formate group is a C 1 ligand with composite structure and high reactivity.It is noteworthy that though separate IR and NMR parameters of Rh(I) carbonyl carboxylate complexes were reported in some of the above-mentioned papers, their comparison is difficult, since they were determined under different conditions. In this work, simple reaction is suggested that can be used to synthesize [ Rh ( µ -HCOO )( CO ) 2 ] 2 complex and its crystal structure is determined. The latter complex is shown to be suitable starting reagent in synthesis of Rh(I) carbonyl hydride HRh ( PPh 3 ) 3 ( CO ) . X-ray diffraction data available in the literature for bis(triphenylphosphine) complexes of the composition transRh ( RCOO )( PPh 3 ) 2 ( CO ) with R = H, CF 3 [13, 17] are supplemented with the data we obtained for analogous acetate complex. IR and NMR measurements of carbonyl formate complexes [ Rh ( µ -HCOO )( CO ) 2 ] 2 and of trans -Rh ( HCOO )( PPh 3 ) 2 ( CO ) together with their acetate and trifluoroacetate analogs made it possible to obtain for the first time a set of comparable spectral parameters that indicates a transfer of electronic effects of the ligands through a central atom. The results of this work were partially reported in the previous publications [20][21][22]. Abstract-Complexes[Rh(µ-RCOO)(CO) 2 ] 2 , where R = H, CH 3 , CF 3 (I, II, III, respectively) are synthesized by reacting anhyd...

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Section: Molecular and Crystal Structure Of [Rh(m-hcoo)(co) 2 ] 2 (I)supporting

confidence: 77%

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

et al. 2005

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“…The Ni-Ni distances amount to 3.72-3.73 Å and the Ni-N distances range from 2.05-2.07 Å for the terminal Ni 2+ ions and from 2.09-2.12 Å (Table 2) for the central Ni 2+ ion. Because the trans influence of nitrogen donor ligands is expected to be higher than that of coordinated water molecules, [22] the Ni-N bond lengths of the central Ni 2+ ion should indeed be somewhat larger than those of the terminal Ni 2+ ions (note that the trans influence is not restricted to square planar compounds [23] ). The Ni-O bond lengths differ to some extent in the two symmetrically inequivalent trinuclear units (values from 2.06-2.08 Å and 2.05-2.11 Å, respectively, Table 2).…”

Section: Introductionmentioning

confidence: 99%

Trinuclear Complexes of Nickel(II) and 4‐Amino‐1,2,4‐triazole

Bräunlich

Medvedev

Dshemuchadse

et al. 2015

Zeitschrift anorg allge chemie

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Abstract. Nickel(II) tetrafluoroborate is capable of forming a variety of complexes with 4-amino-1,2,4-triazole (NH 2 trz), as NH 2 trz can coordinate to one, two, or three Ni 2+ ions and thus can give rise in particular to polynuclear compounds of "infinite" dimensions. From rather concentrated solutions in the presence of an excess of Ni 2+ , however, crystallization of the trinuclear compound [Ni 3 (NH 2 trz) 6 (H 2 O) 6 ](BF 4 ) 6 · 4H 2 O is observed. In this complex, adjacent nickel ions are connected with three bridging NH 2 trz ligands, and three water molecules are bound to each of the terminal nickel atoms. The Ni-N distances at the central Ni 2+ ion were found to exceed those at the terminal Ni 2+ ions, in account with the trans influence of the involved ligands. The dis-

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“…In this contribution we wish to report some results on the coordination of 2-(trimethylsiloxymethyl)phenyl isocyanide (I) and 2-(hydroxymethyl)phenyl isocyanide (II) (Fig. 1) to [Rh 2 (OAc) 4 ] and of (II) to the cationic complex [Rh 2 (OAc) 2 (MeCN) 6 ](BF 4 ) 2 .…”

mentioning

confidence: 99%

Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate

Basato

Biffis

Martinati

et al. 2007

Inorganic Chemistry Communications

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Metal-metal bonding in dirhodium tetracarboxylates. Trans influence and dependence of the rhodium-rhodium bond distance upon the nature of the axial ligands

Cited by 89 publications

References 6 publications

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

Rh(I) carbonyl carboxylato complexes: Spectral and structural characteristics. Some reactions of coordinated formate group

Trinuclear Complexes of Nickel(II) and 4‐Amino‐1,2,4‐triazole

Formation of N-coordinated 4H-benzo[d][1,3]oxazine from 2-(trimethylsiloxymethyl)- and 2-(hydroxymethyl)-phenyl isocyanides promoted by dirhodium(II) acetate

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