Amido Ca and Yb(II) Complexes Coordinated by Amidine-Amidopyridinate Ligands for Catalytic Intermolecular Olefin Hydrophosphination.

A series of amido Ca and Yb(II) complexes LM[N(SiMe)](THF) (1Yb, 1-4Ca) coordinated by amidine-amidopyridinate ligands L were synthesized via a transamination reaction between proligands LH and bisamido complexes M[N(SiMe)](THF) (M = Yb, Ca). The reactions of Yb[N(SiMe)](THF) with proligands LH-LH containing CF and CHF fragments do not allow for preparing the target Yb(II) complexes, while the Ca analogues were synthesized in good yields. Complexes 1Yb and 1-4Ca were evaluated as precatalysts for hydrophosphination of styrene, p-substituted styrenes, α-Me-styrene, and 2,3-dimethylbutadiene with various primary and secondary phosphines (PhPH, 2,4,6-MeCHPH, 2-CNHPH, PhPH, CyPH).

Amido Ln(II) Complexes Coordinated by Bi- and Tridentate Amidinate Ligands: Nonconventional Coordination Modes of Amidinate Ligands and Catalytic Activity in Intermolecular Hydrophosphination of Styrenes and Tolane.

Heteroleptic Ln(II) and Ca(II) amides [tBuC(NC6H3-iPr2-2,6)2]MN(SiMe3)2(THF) (M = Yb (1Yb), Ca (1Ca)), [2-MeOC6H4NC(tBu)N(C6H3-iPr2-2,6)]LnN(SiMe3)2(THF) (Ln = Sm (2Sm), Yb (2Yb)), and [2-Ph2P(O)C6H4NC(tBu)N(C6H3-Me2-2,6)]YbN(SiMe3)2(THF) (3Yb) coordinated by bi- and tridentate amidinate ligands were obtained by the amine elimination reactions of M[N(SiMe3)2](THF)2 (M = Yb, Sm, Ca) with parent amidines in good yields. Complex [tBuC(NC6H3-iPr2-2,6)2]SmN(SiMe3)2 can be obtained only by a salt metathesis reaction of [tBuC(NC6H3-2,6-iPr2)2]SmI(THF)2 with NaN(SiMe3)2. Unlike 1Yb and 1Ca in 1Sm the amidinate ligand is coordinated to metal ion in κ(1)-amido:η(6)-arene fashion preventing THF coordination.