Cyclopentadienyl Complexes of Samarium with Bis(phosphanyl)amides

Abstract

The first heteroleptic bisphosphanylamide complex of the lanthanides, [(η5‐C5Me5)2Sm{η2‐N(PPh2)2}] is reported. [(η5‐C5Me5)2Sm{η2‐N(PPh2)2}] can be obtained by the reaction of the potassium bisphosphanylamide complex, [K(THF)n][N(PPh2)2] (n = 1.25 ‐ 1.5) with [(η5‐C5Me5)2Sm(μ‐Cl)2K(THF)]∞ or in a one‐pot reaction starting from SmCl3 and [K(THF)n][N(PPh2)2] followed by an addition of KC5Me5. Both, [(η5‐C5Me5)2Sm{η2‐N(PPh2)2}] and [(η5‐C5Me5)2Sm(μ‐Cl)2K(THF)]∞ have been characterized by standard analytical/spectroscopic techniques, and their solid‐state structures were established by single crystal X‐ray diffraction.

Bis(phosphinimino)methanides as ligands in divalent lanthanide and alkaline earth chemistry – synthesis, structure, and catalysis

“…Complex 3b shows two sharp signals in the 31 P{ 1 H} NMR spectrum (d 19.8, 49.2 ppm), indicating that the phosphorus atoms of each ligand are chemically equivalent in solution at room temperature. The dynamic behavior of the {(Ph 2 P) 2 N} À ligand was also observed in all other lanthanide complexes reported so far [22,[31][32][33]. Furthermore small satellite signals caused by 2 J(Yb, P) coupling are observed.…”

“…To obtain bis(phosphinimino)methanide amido complexes of the divalent lanthanides we used compounds 2a,b as starting material. As amido ligand we employed the flexible {(Ph 2 P) 2 N} À ligand, which recently was introduced by us into lanthanide chemistry [30][31][32].…”

Open Chain Polyarsenides of the Lanthanides

“…3.087 Å) . The Cg‐Sm (Cg=Cp‐ring centroid) distances (2.400(5) and 2.411(4) Å ( 1 a ) 2.425(2) and 2.513(2) Å ( 1 b )) and the angles Cg‐Sm‐Cg (138.39° ( 1 a ) and 137.08° ( 1 b )) are in the expected range of trivalent samarocene complexes …”

“…[19] The Cg-Sm (Cg = Cp-ring centroid) distances (2.400(5)a nd 2.411(4) (1a)2 .425(2) and 2.513(2) (1b)) and the angles Cg-Sm-Cg (138.398 (1a)a nd 137.088 (1b)) are in the expectedr ange of trivalent samarocene complexes. [31,32] Density functional theory calculations were performed in order to understand the structural change of the (As 2 ) 2 unit in [{Cp'''Co(m,h 2:2 -As 2 )} 2 ]u pon reduction. Instead of the complete molecules, we investigated the model compounds [{CpCo(m,h 2:2 -As 2 )} 2 ]a nd [Cp 2 SmAs 4 (CoCp) 2 ], as wella s K[As 4 (CoCp) 2 ], simulating ac ompletec harget ransfer to the startingm olecule.…”

Highly Strained Heterometallacycles of Group 4 Metallocenes with Bis(diphenylphosphino)amide Ligands

“…N-Binding (Scheme 2, a) is only known in the complexes [( [18]crown-6)Cs{NA C H T U N G T R E N N U N G (PPh 2 ) 2 }] and [(PMDTA)K{NA C H T U N G T R E N N U N G (PPh 2 ) 2 }] (PMDTA = N,N,N',N'',N''-pentamethyldiethylenetriamine), in which additional interactions of the metal with one or two Ph groups, respectively, were observed. [9a,b] N-Binding with an additional P-coordination (Scheme 2, b) was described for numerous rare earth [10][11][12][13] and some alkaline earth metal complexes [12][13][14][15] as well as for the sodium complex [(PMDTA)Na{NA C H T U N G T R E N N U N G (PPh 2 ) 2 }]. [16] This coordination mode was also discussed for the lithium complex [(thf) 3 Li{N-…”