title: Synthesis, structure, and paramagnetism of manganese(II) iminophosphate complexes.
abstract: The coordination chemistry of the bidentate bis(imino)bis(amino)phosphate ligands [Me(3)SiN═P{NR}{N(H)R}(2)](-), where R = n-propyl is [L(1)H(2)](-), R = cyclohexyl is [L(2)H(2)](-), and R = tert-butyl is [L(3)H(2)](-), with manganese(II), is described. The bis(imino)bis(amino)phosphate-manganese(II) complexes [(η(5)-Cp)Mn(μ-L(1)H(2))](2) (1), [Mn(L(2)H(2))(2)]·THF (2·THF), and [(η(5)-Cp)Mn(L(3)H(2))] (3) were synthesized by monodeprotonation of the respective pro-ligands by manganocene, Cp(2)Mn. The molecular structures of 1-3 reveal that the steric demands of the ligand N-substituents play a dominant role in determining the aggregation state and overall composition of the manganese(II) complexes. The coordination geometries of the Mn(II) centers are six-coordinate pseudotetrahedral in 1, four-coordinate distorted tetrahedral in 2, and five-coordinate in 3, resulting in formal valence electron counts of 17, 13, and 15, respectively. EPR studies of 1-3 at Q-band reveal high-spin manganese(II) (S = 5/2) in each case. In the EPR spectrum of 1, no evidence of intramolecular magnetic exchange was found. The relative magnitudes of the axial zero-field splitting parameter, D, in 2 and 3 are consistent with the symmetry of the manganese environment, which are D(2d) in 2 and C(2v) in 3.
authors.affiliation: School of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom.
authors.forename: Daniel N
authors.initials: DN
authors.lastname: Woodruff
authors.forename: Eric J L
authors.initials: EJ
authors.lastname: McInnes
authors.forename: Daniel O
authors.initials: DO
authors.lastname: Sells
authors.forename: Richard E P
authors.initials: RE
authors.lastname: Winpenny
authors.forename: Richard A
authors.initials: RA
authors.lastname: Layfield