Preparative uses of hexaaquaruthenium(II): synthesis of phosphine complexes

Abstract

of the 0 2 2 -ligand being bonded to the boron center in a triangular bidentate (C,) manner,%* and the complex anion [B(02)F3]2-may be a pentacoordinated monomer; however, the possibility that the complex ion is tetrahedral with a terminal 0-0 group cannot be ruled out. The IR spectrum of the complex anion [B2(02)3F2]2-shows a pattern generally similar to that of the [B(O2)F3I2-species, except for much greater broadening of the band a t 1050 cm-'. It is believed that the stereochemistry of boron in the [B2(02),F212-ion is tetrahedral, which is attained through coordination of one 02-ligand in a triangular bidentate fashion, one terminal F ligand, and one end of a bridging 0-0 ligand. An alternate structure of the dimer, similar to that found for NaB03.4H20, with two 0-0 bridges connecting the two boron atoms (Le., a six-membered B204 ring), is also possible irrespective of the mode of coordination of the third peroxide group. In view of the structural study of the complex anion [B2(02)2(OH)4]2-, the latter structure appears more likely. The two extra bands at 3450 (m) and 1640 (m) cm-' in the case of the Na+ and K+ salts were assigned to the vWH and 6 H G H modes of uncoordinated water.9The broad nature of the vSH band in each case indicates a fair possibility of hydrogen bonding through F-H-F interactions. The bans at 1400 (s), 3045 (s), and 3155 (m) cm-' in the spectrum of (NH4)2B2 (02)3F2 have been attributed to the v4, vl, and v3 modes of NH4+. Thus, it is evident from the present work that, under the appropriate conditions, peroxyfluoroborates can be prepared and such complexes are appreciably stable. Acknowledgment. The authors are grateful to the Department of Atomic Energy for generous financial support (Grant No. 37/ 16/82G) and to the reviewers of the paper for valuable suggestions.Registry No. (NH4)2B2(02)3F2, 96455-71-9; Na2B(02)F3, 96455-72-0; K2B(Oz)F,, 96455-73-1. (9) Bhattacharjee, M. N.; Chaudhuri, M. K.; Dasgupta, H. S.; Khathing, D. T.While the chemistry of ruthenium(I1) is vast, many of its complexes fall within two main classifications-chemical complexes containing simple amines as well as 7-accepting heterocycles and molecules containing the wealth of soft ligands associated with organometallic chemistry. RuC13.3H20 ultimately serves as the source of ruthenium in the preparation of many of the compounds within both of these classes. Although the versatility of this starting material is a matter of record, it does suffer two important limitations: (1) a reduction is required in order to obtain Ru(I1) species; (2) the reaction must proceed in the presence of chloride ions. Hexaaquaruthenium(I1) salts may function as alternative starting points for systems where it is desired to avoid either or both of these conditions. The structure of this ion is known,' the lability of the aqua ligands has been studied,2 and a range of solvents is allowed depending upon the choice of anion. The utility of [ R~( H~O )~l ( t o s )~ (tos = ptoluenesulfonate) in the preparation (1) Bernhard, P.; Biirgi, H.-B.; H...

HN2O2− as a Ligand in Mononuclear Hydrogenhyponitrite‐κ2‐N,O Ruthenium Complexes with Bisphosphane Co‐Ligands

“…Room‐temperature powder diffractograms and high‐resolution mass spectra confirmed the formation of pure 1 and 2 , whereby 3 was a mixture of a mainly coarsely crystalline phase and several different microcrystalline phases. Infrared spectra showed sharp signals at 1256 cm −1 ( 1 ) and 1249 cm −1 ( 2 ) for the tosylato ligand (free tosylate: 1200 cm −1 ) . Further analytics (NMR, UV/Vis, IR spectra) confirmed the formation of the complexes 1 – 3 (see the Supporting Information).…”

“…Infrareds pectra showed sharp signals at 1256cm À1 (1)a nd 1249 cm À1 (2)f or the tosylato ligand (free tosylate:1 200 cm À1 ). [23] Further analytics (NMR,U V/Vis, IR spectra)c onfirmed the formation of the complexes 1-3 (see the Supporting Information). For the following reactions, the starting materials were used withoutf urther purification.…”

“…As the starting materials,w eu sed the ruthenium complexes [Ru(dppe) 2 (tos)]BF 4 ·CHCl 3 (1)a nd [Ru(dppp) 2 (tos)]BF 4 ·Et 2 O( 2) both of which exhibit a k 2 O,O' tosylato chelate. Compounds 1 and 2 were synthesized from hexaaquaruthenium(II)t osylate (tos) andt he respective bisphosphanes 1,2-bis(diphenylphosphino)ethane (dppe) [23] and 1,3-bis(diphenylphosphino)propane (dppp;S cheme 3). The products were obtained in crystalline form by using the tetrafluoridoborate counterion and their structures were confirmed by X-ray diffraction.T he ruthenium(II) center was coordinated distorted-octahedrally by two bisphosphanes and at osylato ligand, the latterb eing part of a four-ringc helate (Figure 1a nd Figure2).…”

Trans- and Cis-Water Reactivities in d6 Octahedral Ruthenium(II) Pentaaqua Complexes: Experimental and Density Functional Theory Studies1,2

“…This property allows us to envisage promising research in organometallic chemistry of Ru(II) in water. [Ru(H 2 O) 6 ](tos) 2 is an ideal starting material for a series of new aqua complexes with ligands as varied as N-heterocycles, phosphines, THF, arenes, and olefins 6 and for the facile syntheses of [Ru(H 2 O) 5 L] 2+ (L = N 2 , CO, H 2 CCH 2 9 ).…”

New carboalkoxybis(triphenylphosphine)palladium(II) cationic complexes: Synthesis, characterization, reactivity and role in the catalytic hydrocarboalkoxylation of ethene. X-ray structure of trans-[Pd(COOMe)(TsO)(PPh3)2]·2CHCl3

“…Those at lower frequency suggest the presence of a hydrogen-bond between water and TsO − , with consequent lowering of O-H [31][32][33]. The absorptions in the ranges of 1273-1222, and 1014-1007 cm −1 are identified as some of the characteristic bands of the anionic -SO 3 group [34][35][36][37][38]. The band in the 1037-1025 cm −1 is assignable to the C-O-C stretch of the alkoxycarbonyl group [13,14,24].…”