Substitution of nitrido by the oxo group in reactions of [ReNCl₂(PPh₃)₂] with multidentate N,O^–-donor chelates. Crystal structure of [ReOCl₂(PPh₃)(HL)][H₂L = 2,6-bis(hydroxymethyl)pyridine]

Abstract

The complex [ReNCI,( PPh,),] reacts with the potentially bidentate 8-hydroxyquinoline (Hquin) and N-phenylsalicylideneimine (Hpsal), and potentially terdentate ligands di-2-pyridyl ketone and 2,6-bis( hydroxymethy1)pyridine (H,L) to form the products [ReOCl(quin),], [ReOCI,( PPh,) -(psal)], [ReOCI,{(C,H,N),C(O) (OH)}] and cis-[ReOCI,(PPh,)(HL)], respectively. The first three products are identical t o those isolated earlier by the reactions of trans-[ ReOCI,( PPh,),] with these ligands, while in the latter product the H L -ligand acts as a bidentate N.0--donor, spanning one axial (0trans to Re=O) and one equatorial co-ordination site. These reactions present an alternative synthetic route t o monooxorhenium(v) complexes. The complex cis-[ ReOCI,( PPh,) ( H L)] crystallizes in the orthorhombic space group P2,2,2, with cell parameters a = 10.01 9(3), b = 12.457(6), c = 19.53(1) A , U = 2436.5 A,, Z = 4, R = 0.059 and R' = 0.074 for 1330 reflections with F, > 40(F0).

cis-Dicarbonyl(hydroxydi-2-pyridylmethanolato-κ3N,O,N′)(triphenylphosphine-κP)rhenium(I) dimethyl sulfoxide hemisolvate

“….5dmso, (I), suitable for X-ray analysis were obtained. The facile hydrolysis of N,Nbidentate dpk in cis-[Re(CO) 2 (PPh 3 )(dpk)Cl] is similar to that reported for the hydrolysis of N,N-coordinated dpk in fac-[Re(CO) 3 (dpk)Cl] and other metal complexes containing N,N-bidentate dpk (Bakir & McKenzie, 1997;Gerber et al, 1995).…”

“…The ligand di-2-pyridylmethanone (dpk) and its oxime and hydrazone derivatives are of interest, in part because of their physicochemical properties, reactivity patterns, and applications in many areas, including catalysis, sensors, pharmaceuticals, microelectronics and others (Bernhardt et al, 2003;Camel, 2003;Crowder et al, 2004;Kepert et al, 2004;Kumagai et al, 2003;Sreekanth et al, 2003;Swearingen et al, 2002;Terra et al, 2002). Upon coordination to a variety of metal atoms, dpk undergoes facile hydrolysis to form a gem-diol, which allows for the expansion of monodentate (di-2pyridylmethanone-1 N or -1 O) or bidentate (di-2-pyridylmethanone-2 N,N H ) coordination of dpk to tridentate [hydroxytris(2-pyridyl)methanolato-3 N,O,N H ; Bakir & McKenzie, 1997;Gerber et al, 1995] and tetradentate [tris(2pyridyl)methandiolato-4 N,O,N H ,O] binding (Papaefstathiou et al, 2002). We have been interested in the chemistry of polypyridyl-like compounds of the type (C 5 H 4 N) 2 X, where X = CO, C = NÐOH or C = NHÐNR, and have reported on the synthesis and spectroscopic, electrochemical and structural properties of a series of dpk derivatives and their metal complexes (Bakir & McKenzie, 1997;Bakir, Brown & Johnson, 2004;Bakir, Hassan et al, 2004;Bakir & Brown, 2003;Bakir et al, 2003;Bakir, 2002a,b,c;Bakir, 2001a,b).…”

The optical sensorfac-tricarbonylchloro(di-2-pyridylmethanonep-nitrophenylhydrazone)rhenium(I) dimethyl sulfoxide solvate

“…The N,N-chelating dpknph molecule forms a six-membered Re1ÐN1ÐC15Ð CÐC25ÐN2 metallocyclic ring in a boat conformation. The NÐReÐN bite angle of 83.32 (12) is of the same order as those reported for tricarbonylrhenium compounds of N,Nbidentate polypyridyl-like ligands containing six-membered rings (Bakir, 2001;Gerber et al, 1993Gerber et al, , 1995. For example, an NÐReÐN bite angle of 84.6 (4) was reported for dpkO,OH in [ReOCl 2 (dpkO,OH)] (Gerber et al, 1993(Gerber et al, , 1995 and a bite angle of 80.27 (19) was observed for dpkÁoxime in fac-[ReCl(dpkÁoxime)(CO) 3 ]ÁDMSO (Bakir, 2001).…”

Rhenium(V) Oxo Complexes with Acetylacetone Derived Schiff Bases: Structure and Catalytic Epoxidation

“…45 In addition, in the previously reported Compounds 1 and 2 should be compared to previously reported structures of the type [ReO(LL′)Cl 2 (PPh 3 )] where LL′ represents either a monoanionic bidentate ligand or two monodentate ligands one of them being monoanionic and the other one neutral. 6,12,[47][48][49][50][51] In all reported compounds, the oxygen donor is located trans to the oxo group, but the position of the chlorine atoms relative to each other differ being either trans as found in 1 and 2 or cis as found in the majority of the structures. The trans-Cl,Cl conformation has only rarely been found in this type of complex.…”