Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac-Re(NBBr3)Br3(Me2PhP)2]

Schmidt-Brücken, B.; Abram, Ulrich

doi:10.1002/1521-3749(200108)627:8<1714::aid-zaac1714>3.0.co;2-w

Cited by 9 publications

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“…Currently, the Cambridge Structural Database contains 452 rhenium complexes with terminal bromides, and only four 16 of these have Re−Br bonds longer than 2.714 Å. In mononuclear complexes, the longest Re−Br bond, 2.795 Å, is found in cis - ReBr 2 (⋮N)(PMe 2 Ph) 3 , trans to the nitrido ligand; the other Re−Br bond in this complex is normal and much shorter, 2.587 Å 16b…”

Section: Resultsmentioning

confidence: 99%

Hydridic Rhenium Nitrosyl Complexes with Pincer-Type PNP Ligands

2007

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The hydride complexes ReHBr (NO)[HN(C 2 H 4 PR 2 ) 2 ] (R ) Pr i , 1a; Bu t , 1b) were synthesized by reactions of [NEt 4 ] 2 [Re(NO)Br 5 ] with the pincer-type ligands HN(C 2 H 4 PR 2 ) 2 . Treatment of 1a and 1b with Bu t OK led to their dehydrobromination, resulting in the amido hydrides ReH(NO)[N(C 2 H 4 PR 2 ) 2 ] (2a,b), respectively. The dihydride trans-ReH 2 (NO)[HN(C 2 H 4 PPr i 2 ) 2 ] (3a) was obtained by stirring an ether solution of 2a under hydrogen. Similarly, partial conversion of 2b was achieved under hydrogen to give trans-ReH 2 (NO)[HN(C 2 H 4 PBu t 2 ) 2 ] (3b). The structure and properties of complexes 1-3 were studied by DFT calculations. Complexes 2a and 3a demonstrated low activity for transfer hydrogenation of acetophenone and cyclohexanone due to instability in 2-propanol.

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Section: Resultsmentioning

confidence: 99%

Hydridic Rhenium Nitrosyl Complexes with Pincer-Type PNP Ligands

2007

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Reactive Transition Metal Nitride Complexes

Smith

2014

Progress in Inorganic Chemistry

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Reactions of Rhenium and Technetium Nitrido Complexes with ER₃ Fragments (E = B, Ga, Al, C, P; R = H, Alkyl, Aryl)

Abram

Schmidt-Brücken

Hagenbach

et al. 2003

Zeitschrift anorg allge chemie

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Terminal ‘N3—’ ligands in rhenium and technetium nitrido complexes are sufficiently nucleophilic to react with Lewis acids under formation of nitrido‐bridged compounds. The reactivity of the nucleophilic centre and the nature of the formed compounds are strongly dependent on the Lewis acid and the composition of the metal complex used. Air‐stable compounds with Re≡N‐ER3 bridges are formed when ER3 is BR3 (R = H, Cl, Br, Ethyl, Phenyl, C6F5), BCl2Ph, GaCl3, CPh3+, or PPh3. The six‐co‐ordinate rhenium(V) complexes [ReNX2(PMe2Ph)3] (X = Cl, Br), [ReN(X)(Et2dtc)(PMe2Ph)2] (Et2dtc— = diethyldithiocarbamate) and [ReN(Et2dtc)2(PMe2Ph)] have been proved to be excellent starting materials for this type of reactions, whereas the five‐co‐ordinate precursors [ReNCl2(PPh3)2], [ReN(Et2dtc)2], [ReN{Ph2P(S)NP(S)Ph2}2] or [ReNCl4]— only react with the most reactive Lewis bases of the examples mentioned above such as BCl2Ph or B(C6F5)3. The rhenium‐nitrido bond lengths remain almost unchanged by the adduct formation, whereas a significant decrease of the trans‐influence of the nitrido complexes has been observed as can be seen by a shortening of the corresponding bond lengths or dimerization of five‐co‐ordinate precursors. Electrophilic attack of the Lewis acid to a donor atom of the equatorial co‐ordination sphere of the rhenium complex results in the formation of ‘underco‐ordinate’ metal centres which resemble to di‐, tri or tetrameric units with asymmetric nitrido bridges between each two rhenium atoms. EPR spectroscopy is an excellent tool to reflect the formation of nitrido bridges at the paramagnetic (d1) [ReNX4]— core (X = F, Cl, Br, NCS). The spectral parameters derived for the products of reactions of [ReNCl4]— with various boron compounds indicate an increase of the covalency of the equatorial Re‐L bonds as a consequence of the formation of a nitrido bridge. The tendency for the formation of nitrido bridges with Lewis acids is significantly lower for technetium compounds compared to their rhenium analogues. Only a few examples with BH3 and BPhCl2 have been established.

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Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac-Re(NBBr3)Br3(Me2PhP)2]

Cited by 9 publications

References 2 publications

Hydridic Rhenium Nitrosyl Complexes with Pincer-Type PNP Ligands

Hydridic Rhenium Nitrosyl Complexes with Pincer-Type PNP Ligands

Reactive Transition Metal Nitride Complexes

Reactions of Rhenium and Technetium Nitrido Complexes with ER₃ Fragments (E = B, Ga, Al, C, P; R = H, Alkyl, Aryl)

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Synthese und Strukturen von [ReNBr2(Me2PhP)3] und (Me2PhPH)[fac-Re(NBBr3)Br3(Me2PhP)2]

Cited by 9 publications

References 2 publications

Hydridic Rhenium Nitrosyl Complexes with Pincer-Type PNP Ligands

Hydridic Rhenium Nitrosyl Complexes with Pincer-Type PNP Ligands

Reactive Transition Metal Nitride Complexes

Reactions of Rhenium and Technetium Nitrido Complexes with ER3 Fragments (E = B, Ga, Al, C, P; R = H, Alkyl, Aryl)

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Reactions of Rhenium and Technetium Nitrido Complexes with ER₃ Fragments (E = B, Ga, Al, C, P; R = H, Alkyl, Aryl)