Preparation and molecular structure of TaH[P(C6H5)2]2[(CH3)2PC2H4P(CH3)2]2, a metal hydride of the type MHL2(bidentate phosphine)2n+ having a pentagonal-bipyramidal structure

Dimorphism in Actinide Phosphides: Tetrakis[bis(2-dimethylphosphinoethyl)phosphido]thorium(IV)

“…The difference between the average lengths of the formally anionic phosphidothorium bonds and the formally neutral phosphinothorium bonds is as expected (Domaille, Foxman, McNeese& Wreford, 1980). Fig.…”

Syntheses, Crystal Structures and Reactivity of Organometallic Tantalum(IV) Phosphinidene Complexes: trans-[{Cp*TaCl(μ-PR)}2] (Cp* = C5Me5, R = Cy, tBu, Ph), cis- and trans-[{Cp*TaCl(μ-PMes)}2] (Mes = 2,4,6-Me3C6H2) and cis-[{Cp′TaCl(μ-PMes)}2] (Cp′ = C5H4Me)

“…However, in solution the four isocyanide ligands are equivalent ( 13 C NMR). 4 ]Cl (7) (ORTEP plot, 50% probability, SHELXTL PLUS; XP [37] ). As the TaϪC bond lengths of the isocyanide ligands [2.179(4) to 2.187(4) Å ] are in the range of TaϪC single bonds and the CϪNϪC(Cy) groups are almost linear [165.6(4)°to 175.5(4)°], mesomeric structure A can be assumed.…”

“…[1] To date, only a few phosphanido derivatives of organometallic [2,3] and inorganic [4,5] tantalum compounds, one phosphinidene-bridged dimeric Ta IV complex [3] and two stable terminal phosphinidene complexes [5,6] have been described in the literature.…”

“…However, when [Cp* TaCl 4 (PH 2 R)] (R ϭ tBu, Cy, Ad, Ph, Mes) were treated with DBU an internal redox reaction occurred with formation of [(DBU)H][Cp*TaCl 4 ] (DBU ϭ 1,8-diazabicyclo [5.4.0]undec-7-ene) and the corresponding diphosphane (P 2 H 2 R 2 ) or decomposition products thereof. [8] For the aryl-substituted phosphane complexes, there was also an in- 4 ]Cl (7), which was characterised by 1 H and 13 C NMR spectroscopy and by crystal structure determination. As a minor product, [(Cp*TaCl 2 ) 2 (µ 2 -O)(η 2 ,µ 2 -P 2 Cy 2 )] (8) was also obtained in the reaction of [Cp*TaCl 4 ] with LiPHCy.…”

Stepwise Sulfuration of the Terminal Phosphido Complex trans‐[PtCl(PHCy2)2(PCy2)]: Synthesis of [Pt(κ2S,S′‐PS2Cy2)(PHCy2)2]Cl and [Pt(κ2S,S′‐PS2Cy2){κP‐P(S)Cy2}(PHCy2)] and Crystal Structure of [Pt(κ2‐S,S‐PCy2S2)(κ‐S‐PCy2S2)(PHCy2)]

“…The first terminal phosphido complexes were prepared in 1968 by reaction of CpFe(CO) 2 -or CpMo(CO) 3 -with P(C 6 F 5 ) 2 Cl to give Cp(CO) 2 Fe[P(C 6 F 5 ) 2 ] and Cp(CO) 3 Mo[P(C 6 F 5 ) 2 ], respectively. [1] From then on, a number of terminal phosphido complexes have been prepared mainly by two routes: (i) the reaction of diorganometal phosphides with a metal species; [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] (ii) the deprotonation of a coordinated phosphane bearing at least a P-H bond by means of an appropriate base {1,8-diazabicyclo [5.4.0]undec-7-ene (DBU), [17][18][19] methoxide, OH -, [20][21][22][23][24] tBuO -, [25][26][27][28][29] [N(SiMe 3 ) 2 ] -, [30][31][32] NEt 3 , [33] BuLi [34] } that, in some instances, was previously coordinated onto the metal atom. [35][36][37][38][39]...…”