ChemInform Abstract: PREPARATION, PROPERTIES AND CRYSTAL STRUCTURE OF RHENIUM(VII) NITRIDE CHLORIDE, RENCL4

Liese, W; Dehnicke, Kurt; Walker, Ian M.; Straehle, J.

doi:10.1002/chin.197931038

Cited by 3 publications

(3 citation statements)

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“…With regard to this aspect various structures are known. [34][35][36][37] Also our considerations do not give an answer to possible [NWCl 3 ] ∞ polymerization, 8 as has been found for NReCl 4 38 and NW(t-BuO) 3 . 39 It is of interest to extend the considerations to d 7 and d 8 transition elements.…”

Section: Discussionmentioning

confidence: 56%

Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor−Acceptor Formation

Schoeller

Sundermann

1998

Inorg. Chem.

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According to quantum chemical calculations, nitrido chlorides constituted from d6 transition metals form ring structures which are best described as weak donor−acceptor complexes between the lone pair at nitrogen and the empty d orbitals at the transition metal. The stabilities of the ring structures increase in the order Cr < Mo < W. The transition metal Cr forms only endothermic ring systems, and these in turn decompose into monomers. A comparison of several homologous oligomers of NMoCl3 shows maximum stability for the tetramer, in agreement with the experimental findings. This particular stability of the tetramer is due to a perfect alignment of the nitrogens between two metal centers. The vibrational analyses reveal that the character of the monomers is nearly conserved in the ring systems. An analysis of the electron densities on the basis of Bader's method of atoms in molecules as well as of the natural bond orbitals (NBO) substantiates the weak ring stabilities.

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Section: Discussionmentioning

confidence: 56%

Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor−Acceptor Formation

Schoeller

Sundermann

1998

Inorg. Chem.

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“…For example, calculations suggest that metallonitride polymers with d n > d 2 will adopt symmetrically bridged structures 56 rather than the very asymmetrically bridged structures found to date for structurally characterized linear chain metallonitrides. [57][58][59][60][61][62][63][64][65] More generally, control over the nature of M(N)M interactions should be possible via control of the metal electron count and electronic structure. These ideas, plus our longstanding interest in the nitrido ligand as a bridging group to link transition metals in polynuclear, oligomeric, and polymeric species, 5-7,65-68 sparked our interest in the study of electron-rich polynuclear metallonitrides.…”

Section: Introductionmentioning

confidence: 99%

Electron-Rich Nitrido-Bridged Complexes. Structure and Bonding in Triosmium Dinitrido Compounds

1999

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Triosmium dinitrido-bridged compounds Os3(N)2Cl8L6 (L = 3-picoline, 4-ethylpyridine, 4-tert-butylpyridine) have been prepared via the thermolysis of the terminal nitrido complexes Os(N)Cl3L2. X-ray structural studies of Os3(N)2Cl8(4-Etpy)6 and Os3(N)2Cl8(4-t-Bupy)6 reveal a linear Os3(N)2 unit with multiple bonding significantly localized in the outer osmium−nitrogen bonds in OsV⋮NOsIVN⋮OsV. A simple model of bonding and electronic structure consistent with the solid-state structures is discussed.

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“…However, the distance of Cs+ to the nearest sulphate oxygens is 3.08-3.24 A. (Liese et al 1979). All of these other separations are found in neutral species, without constraints due to the presence of alkali-metal cation/crown ether complexes in the crystal lattice.…”

Section: Discussionmentioning

confidence: 98%

Preparation and ESR studies of salts of crown ether complex cations and nitridotechnetium(VI) anions: structures of the twinned ‘infinite sandwich’ [Cs(18-crown-6)][TcNCl ₄ ] complex and of [Rb(15-crown-5) ₂ ] [TcNCl ₄ (OH ₂ )]

1993

Proc. R. Soc. Lond. A

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We report the preparations and electron spin resonance (ESR) studies of a series of Cs + and Rb + crown ether (15-crown-5 and 18-crown-6) salts of [TcNCl 4 ] - and [MoOCl 4 ] - , and a new refinement of the X-ray structure of [Cs(18-crown-6)] [TcNCl 4 ] involving a twinned P4/n scattering model. This refinement addresses some unsatisfactory aspects of the original disordered model. The structure consists of an ‘infinite sandwich’ Cs + cation/crown ether configuration and polymeric [TcNCL 4 ] - anions, with Tc≡N distances of 1.561(36) Å, and anti-parallel chains of –––Tc≡N–––Tc≡N –––with Tc···Tc separations of 4.275(4) Å. The structure determination of [Rb(15-crown-5) 2 ][TcNCl 4 (OH 2 )] is also described and shows a lattice containing 2:1 ‘sandwich’-type crown ether/alkali-metal cations and isolated anions in the disordered lattice. The presence of Tc≡N infrared stretching frequencies at ca . 1074 cm -1 indicates the absence of strong electron donors coordinated to Tc in the sixth position (i. e. isolated anions), whereas the polymeric chain structure of [Cs(18-crown-6)] [TcNCL 4 ] is characterized by a Tc≡N stretching frequency of 1041 cm -1 . Three product compounds, the ‘infinite sandwich’ [Cs(18-crown6)][TcNCl 4 ], [Cs(18-crown-6)] [TcNCL 4 (OH 2 )] with two Tc≡N stretching frequencies at 1055 and 1046.5 cm -1 , and [Cs(18-crown-6) 2 ][TcNCl 4 containing 2:1 crown ether/Cs + ‘sandwich’ cations and isolated [TcNCl 4 ] - anions, could be obtained from reaction of Cs + /18-crown-6 and [TcNCL 4 ] - depending on reaction conditions and solvent. The ESR spectra of [Cs(18-crown-6)] [TcNCl 4 ] over the temperature range 130-290 K indicate the presence of exchange interactions along the linear ––– Tc≡N––– Tc≡N––– chains. Spectra for other crown ether salts are consistent with isolated [TcNCL 4 ] - or [TcNCL 4 (OH 2 )] - anions, with dipolar broadening effects apparent.

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ChemInform Abstract: PREPARATION, PROPERTIES AND CRYSTAL STRUCTURE OF RHENIUM(VII) NITRIDE CHLORIDE, RENCL4

Abstract: Reaktion von ReCls mit NCl3 in CCl4 führt zu der metallisch glänzenden Titelverbindung (III), die sehr hygroskopisch ist und ein magnetisches Moment von 0.23 B.M.

Cited by 3 publications

References 1 publication

Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor−Acceptor Formation

Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor−Acceptor Formation

Electron-Rich Nitrido-Bridged Complexes. Structure and Bonding in Triosmium Dinitrido Compounds

Preparation and ESR studies of salts of crown ether complex cations and nitridotechnetium(VI) anions: structures of the twinned ‘infinite sandwich’ [Cs(18-crown-6)][TcNCl ₄ ] complex and of [Rb(15-crown-5) ₂ ] [TcNCl ₄ (OH ₂ )]

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ChemInform Abstract: PREPARATION, PROPERTIES AND CRYSTAL STRUCTURE OF RHENIUM(VII) NITRIDE CHLORIDE, RENCL4

Abstract: Reaktion von ReCls mit NCl3 in CCl4 führt zu der metallisch glänzenden Titelverbindung (III), die sehr hygroskopisch ist und ein magnetisches Moment von 0.23 B.M.

Cited by 3 publications

References 1 publication

Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor−Acceptor Formation

Ring Structure Formation in Transition-Metal Nitrido Chlorides by Donor−Acceptor Formation

Electron-Rich Nitrido-Bridged Complexes. Structure and Bonding in Triosmium Dinitrido Compounds

Preparation and ESR studies of salts of crown ether complex cations and nitridotechnetium(VI) anions: structures of the twinned ‘infinite sandwich’ [Cs(18-crown-6)][TcNCl 4 ] complex and of [Rb(15-crown-5) 2 ] [TcNCl 4 (OH 2 )]

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Preparation and ESR studies of salts of crown ether complex cations and nitridotechnetium(VI) anions: structures of the twinned ‘infinite sandwich’ [Cs(18-crown-6)][TcNCl ₄ ] complex and of [Rb(15-crown-5) ₂ ] [TcNCl ₄ (OH ₂ )]