Characterisation of three isomers of trans-[IrCl2(EMe2Ph)4]ClO4(E = P or As) each containing adjacent parallel phenyl rings

Abstract

parallel phenyl rings leading to 1H n.m.r. (phenyl) resonances as high-field as 6 5.7.Unexplained features of n.m.r. spectra of several transoctahedral complexes containing four PMe2Ph ligands in a plane have been described.1-3 A broad 1H n.m.r. Me singlet at room temperature has been reported for trans-[IrC12(P-Me2Ph),]+ (1)1 and one PMe2Ph ligand in the isoelectronic trans-[OsC12(PMe2Ph)4] was thought to be unique, possibly co-ordinated through the phenyl group agostically or by n-complexation? We now show that the Ir complex contains four M-P bonds and that the n.m.r. effects result from the presence of rotamers in exchange, each containing at least two phenyl groups in close parallel alignment. The complexes trans-[IrC12(EMe2Ph)4][C104], (1, E = P) and (2, E = As) were prepared as yellow crystals by treating trans, rner-[IrC12(H20)(EMe2Ph)3][C104]4 with EMe2Ph. The single-crystal X-ray structure of (1) (Figure l)t shows that two ~ t Crystal data for compound (1): C32H44C131r04P4, M = 915.19, monoclinic, space group n 1 / c , a = 11.185(2), b = 26.301(2), c =

Multinuclear and Dynamic NMR Study of trans-[Pt(Cl)(PHCy2)2(PCy2)], [Pt(Cl)(PHCy2)3][BF4], [Pt(Cl)(PHCy2)3][Cl], trans-[Pt(Cl)(PHCy2)2{P(S)Cy2}], and trans-[Pt(Cl)(PHCy2)2{P(O)Cy2}]. Influence of Intramolecular PO···H−P and Cl···H−P Interactions on Restricted Rotation about Pt−P Bond. X-ray Structure of trans-[Pt(Cl)(PHCy2

“…10 Dynamic Behavior of 2, 3, and 4. To confirm our assignment of ∆G q predominantly to the rotational process, we decided to compare the dynamic behavior of 1 with that of complexes [Pt(PHCy 2 ) 3 Cl]BF 4 …”

Diazo Complexes of Rhenium: Preparations and Crystal Structures of the Bis(dinitrogen), [Re(N2)2{PPh(OEt)2}4][BPh4] and Methyldiazenido [ReCl(CH3N2)(CH3NHNH2){PPh(OEt)2}3][BPh4] Derivatives

“…However, the 31 P spectra may also be interpreted on the basis of a trans geometry, in which the four PPh(OEt) 2 ligands are made inequivalent by the different arrangement of the phenyl and ethoxy groups of one phosphite with respect to the other. Examples of inequivalent phosphorus nuclei in octahedral complexes containing four PPhMe 2 or PPh(OEt) 2 ligands in a plane were recently reported for [IrCl 2 (PPhMe 2 ) 4 ]ClO 4 , FeHCl[PPh(OEt) 2 ] 4 , and MnH(CO)[PPh(OEt) 2 ] 4 derivatives. Taking into account these precedents and the crystal structure shown in Figure , discussed below, we find that the trans octahedral geometry VII (Scheme 2) may also be proposed in solution for the [ReCl(PhN 2 ){PPh(OEt) 2 } 4 ][BPh 4 ] compound ( 7 ).…”

Synthesis, Characterization, and Reactivity of Cationic Molecular Hydrogen Complexes of Manganese(I)

“…However, the 31 P spectra may also be interpreted on the basis of the presence of a trans geometry ( III ), in which the four PPh(OEt) 2 phosphite ligands are made inequivalent by the different arrangement of the phenyl and ethoxy groups of one phosphite with respect to the other. Examples of inequivalent phosphorus nuclei in octahedral complexes containing four PPhMe 2 or PPh(OEt) 2 ligands in a plane have recently been reported for [IrCl 2 (PPhMe 2 ) 4 ]ClO 4 and FeHCl[PPh(OEt) 2 ] 4 derivatives. Taking into account these precedents and the fact that the related MnH(CO)[P(OEt) 3 ] 4 ( 3a ) complex containing the P(OEt) 3 ligands shows, in solution, a trans geometry, we find that a similar trans octahedral geometry can also be proposed for the MnH(CO)[PPh(OEt) 2 ] 4 ( 3b ) species.…”