The approach to 4d/4f-polyphosphides

Abstract

The first 4d/4f polyphosphides were obtained from reactions of the divalent metallocenes [Cp*2Ln(thf)2] (Ln = Sm, Yb) with [{CpMo(CO)2}2(μ,η2:2-P2)] or [Cp*Mo(CO)2(η3-P3)]. New aggregation of the central phosphorus scaffold in combination with P–P bond formation within the coordination sphere of the transition metal was observed.

Reductive Trapping of [(OC)5W–W(CO)5]2− in a Mixed‐Valent SmII/III Calix[4]pyrrolide Sandwich

“…The two kinds of C−O bonds show intense stretching vibrations, respectively at 1668 cm −1 (isocarbonyl) and 1899, 1923, and 1946 cm −1 (terminal carbonyl) in the IR spectrum. Similar behavior has been observed in relevant compounds, for example, [(Cp* 2 Sm) 2 P 6 (Cp*Mo(CO) 2 ) 2 ] and [(Tp Me,Me ) 2 Sm( μ ‐CO)(CpCr(CO) 2 )] . The carbonyl groups have displayed CO bands at 1885, 1967, and 2073 cm −1 in the Raman spectrum.…”

Recent Advances in Rare‐Earth Polypnictides

“…Additionally, dual P—P bond formation in one reduction step has been observed in the reaction between {CpMo(CO) 2 } 2 ‐ (μ,η 2:2 ‐P 2 ) and Cp* 2 Ln(THF) 2 (Ln = Sm, Yb), affording tetra‐ and hexa‐nuclear structural motifs as minor products (Figures C and D) . Compared to those known polyphosphides, such as [CuBr(Cp 2 Mo 2 (CO) 4 P 2 )] n and [{(CpMo(CO) 2 P 2 } 4 Ag 2 ][Al{OC(CF 3 ) 3 } 4 ] 2 , the structure of [CpMo(CO) 2 P 2 ] unit is not destroyed in tetra‐ and hexa‐nuclear structural motifs, because the reduction activity of [Cp* 2 Eu(THF) 2 ] is too weak to cleave the Mo—P bonds.…”

“…This reaction was rationalized as a result of initial cobalt reduction by samarocene: the redistribution of local charges in the Co 2 (μ,η 2:2 ‐P 2 ) 2 core induced the P—P bond formation accompanied with minimal geometrical changes. Similarly, when Cp*Mo(CO) 2 (η 3 ‐ cyclo ‐P 3 ) was treated with [Cp* 2 Ln(THF) 2 ] (Ln = Sm, Yb), P—P bond formation was triggered, furnishing a tetranuclear structure (Cp* 2 Ln) 2 P 6 (Cp*Mo(CO) 2 ) 2 with a coupled cyclo ‐P 3 linkage (Figure B) …”

“…However, when the same reaction of Cp* 2 Sm with Sb/Hg amalgam was carried out at 60—70 °C, a mercury‐containing compound [(Cp* 2 Sm) 3 (μ 4 ‐ŋ 1:2:2:2 ‐Sb 4 )] 2 Hg (Figure C) could be harvested, shedding light on the formation mechanism of polystibides. The Sb 4 units in both ( ŋ 5 ‐Cp' 2 Dy) 3 [μ‐(SbMes) 3 Sb}] and [(Cp* 2 Sm) 3 (μ 4 ‐ŋ 1:2:2:2 ‐Sb 4 )] 2 Hg are markedly different from planar [Pn 4 ] 2– (Pn=P, As, Sb and Bi) squares with 6π electrons and slightly distorted Sb 4 planar unit with 4π electrons. This compound containing two [(Cp* 2 Sm) 3 Sb 4 ] – fragments bridged by a Hg 2+ , represented the first example of a ternary Sb/Hg compound with Sb—Sb bond lengths ranging from 2.8160(9) to 2.8672(9) Å, in accordance with those found in {( i‐ Pr) 2 NC‐[N(2,6‐( i ‐Pr) 2 C 6 H 3 ] 2 Mg} 4 Sb 4 …”

Isolation and Characterization of a Trinuclear Rare-Earth Metal Complex Containing a Bicyclo[3.1.0]-P64- Ligand

“…[12] Later, a binuclear niobium complex bearing c P 3 -c P 3 ; ligand was documented (Scheme 1c). [13] Besides P 6 ligands derived from P 4 , a 3d/4f complex having c P 3 -c P 3 ligand [14] (Scheme 1c) and these complexes bearing linear 6 6 Por 4 6Pligands [15,16] (Scheme 1d) could also be obtained by other methods. Although four types of P 6 ligands have been reported, the new type of bicyclo[3.1.0]-4 6 Pligand is unexplored (Scheme 1e).…”