F.A. Hart

Lanthanide complexes—IV: Complexes of triphenylphosphine oxide with lanthanide and yttrium nitrates

Abstract Triphenylphosphine oxide reacts with lanthanide and yttrium nitrates in organic solvents to give complexes M(NO 3 ) 3 L 2 EtOH, M(NO 3 ) 3 L 3 , M(NO 3 L 3 (Me 2 CO) 2 , M(NO 3 ) 3 L 4 Me 2 CO, M(NO 3 ) 3 L 4 EtOH and [M(NO 3 ) 2 L 4 ]NO 3 , where M is a lanthanide or yttrium and L is Ph 3 PO. Properties, reactions and spectra are discussed in terms of possible structures and the nature of the bonding.

Lanthanide complexes—III: Complexes of 2,2′-dipyridyl with lanthanide chlorides, thiocyanates, acetates and nitrates☆

Abstract Well-crystalline complexes of the novel types MCl3(dipy)H2O, M(CH3COO)3(dipy), MCl3(dipy)2, MCl3(dipy)2EtOH and M(CNS)3(dipy)3 are reported and described (M = a lanthanide and dipy = 2,2′-dipyridyl). Further data are presented concerning the complexes M(NO3)3(dipy)2, and all the complexes are compared with the corresponding 1:10-phenanthroline compounds with respect to possible structures and relative stability.

Lanthanide complexes-VIII tris(2,2′6′,2″-terpyridine)lanthanide(III)perchlorates: Fluorescence and structure

Abstract Complexes [M(terpy)3](ClO4)3 (M = a lanthanide and terpy = 2,2′6′,2″-terpyridine) has been isolated. Their properties, including the fluorescence spectrum of the europium complex, support their formulation as nine-coordinate amine complexes; the cation having slightly distorted D3 symmetry.

Lanthanide complexes—VII: Complexes of yttrium and lanthanide chlorides and thiocyanates with triphenylarsine oxide and triphenylphosphine oxide

Yttrium and the lanthanide chlorides and thiocyanates form complexes of the types MCl3(OPPh3)3, MCl3(OPPh3)4, M(NCS)3(OPPh3)3, M(NCS)3(OPPh3)4 and M(NCS)3(OAsPh3)3. Infra-red spectra in the region 4000-200 cm−1 are reported. Dissociative equilibria in solution have been investigated and possible structures are discussed.

Lanthanide complexes—II: Complexes of 1:10-phenanthroline with lanthanide acetates and nitrates☆

Abstract Well-crystalline, thermally stable complexes of the types M(CH 3 COO) 3 (phen) and M(NO 3 ) 3 (phen) 2 , where M = all the lanthanides except Pm and phen = 1:10-phenanthroline, have been isolated. Magnetic moments and infra-red spectra are reported and structures are discussed.

Lanthanide complexes—X: PMR studies of alkyl-substituted bipyridine complexes of lanthanides: Paramagnetic shifts and reaction kinetics

Abstract The proton magnetic resonance spectra of the complexes [M(NO3)3L2] and [M(NO3)3L2′] (M = a lanthanide or Y; L = 4,4′-di-n-butyl-2,2′-bipyridine; L′ = 5,5′-di-n-butyl-2,2′-bipyridine in chloroform solution show paramagnetic shifts whose origin is probably a combination of contact and pseudo-contact processes. These shifts permit measurement of the thermodynamic parameters of an exchange reaction: MX 3 L 2 +L ∗ →MX 3 LL ∗ +L which is shown to proceed by a dissociative mechanism.

Lanthanide complexes—VI. Complexes of yttrium and lanthanide thiocyanates, chlorides, nitrates and salicylates with 1,2-bis(pyridine-α-aldimino)ethane

Abstract Solid complexes of the type MX 3 L have been prepared ( M = a lanthanide or yttrium; X  Cl, NO 3 , NCS or 2-OH.C 6 H 4 .COO; L  C 5 H 4 N:CH:N CH 2 CH 2 N:CH.C 5 H 4 N). Their i.r. (4000-200 cm −1 and electronic spectra and other properties are discussed in relation to proposed structures. In aqueous solution a fairly stable species [M(C 14 H 14 N 4 ) 2 ] 3+ predominates.

Lanthanide complexes—V complexes of yttrium and lanthanide nitrates with triphenylarsine oxide☆

Complexes of triphenylarsine oxide with yttrium and lanthanide nitrates have been prepared and studied. The following stoichiometries were obtained: M(NO3)3(OAsPh3)2EtOH, M(NO3)3(OAsPh3)3 and M(NO3)3(OAsPh3)4. Triphenylarsine oxide is more strongly bound to these metal ions than is triphenylphosphine oxide; the metal-ligand bond is almost entirely of an ion-dipole character. The i.r. spectra are discussed, especially with respect to the detailed behaviour of vaso.

Lanthanide complexes—IX: Complexes of lanthanide salts with dibutylbipyridines

Abstract Lanthanide nitrates, thiocyanates and chlorides form complexes, soluble in inert organic solvents, with the new ligands 4,4′-di- n -butyl-2,2′-bipyridine and 5,5′-di- n -butyl-2,2′-bipyridine. Structures and bonding are discussed in the light of colligative measurements, i.r. spectra, and electronic spectra in absorption and fluorescence.