Triphosphane formation from the terminal zirconium phosphinidene complex [Cp2ZrPDmp(PMe3)] (Dmp=2,6-Mes2C6H3) and crystal structure of DmpP(PPh2)2

Syntheses of a stable tristibine and of related antimony compounds with the 2,6-dimesitylphenyl (Dmp) substituent

“…The reaction of DmpMgBr and PhSbCl 2 gives Dmp(Ph)-SbBr (3). Reaction of 3 with LiAlH 4 leads to the chiral secondary stibine Dmp(Ph)SbH (5). Attempts to obtain the tristibine DmpSb[Sb(Ph)Dmp] 2 by UV photolysis of solutions containing stoichiometric mixtures of 4 and 5 were not successful due to the stability of 5 under these conditions.…”

“…The stable distibenes: (RSb) 2 R = Dmp or 2,6-Trip 2 C 6 H 3 [1], the hydrides DmpSbH 2 (4) [2], RSbH 2 and RSb(Li)H, R = 2,6-Trip 2 C 6 H 3 [3], and their precursors DmpSbCl 2 [1,4] and 2,6-Trip 2 C 6 H 3 SbCl 2 [1] were obtained. The Dmp group was also used to protect the P 3 unit in DmpP(PPh 2 ) 2 [5].…”

“…Thermal ellipsoid representation (30%) of dimeric units in the structure Dmp(Ph)SbH(5). The carbon bonded hydrogen atoms were omitted for clarity.…”

Nucleophilic Phosphinidene Complexes: Access and Applicability

“…[21] Salt metathesis and Lewis base stabilization also enabled the synthesis of hafnium phosphinidene [Cp 2 (Me 3 P)Hf=PÀMes*] (6), [22] the terminally bonded phosphinophosphinidene complex [Cp 2 (PhMe 2 P)Zr = P À PtBu 2 ] (7), [23] and the uranium [24] For all of these compounds, bent M = P À R bonding is indicated by 31 P NMR spectroscopic data (6 d = 671, 7 728, 8 71 ppm) and solid-state structures (M-P-C/P 7 115.53 (16), 8 143.7(3) ).…”

Synthesis, structure, and reactivity of platinum compounds featuring terminal amido and phosphido ligands

“…Isolated terminal phosphinidene complexes are known with a Mes ⁄ (or highly related 2,4, 6-i Pr 3 C 6 H 2 [48]) protected phosphorus for transition metals including Ti, Zr, V, W, Ru, Os, Co, Rh, and Ir [20]. Terminal phosphinidene ligands featuring the dmp substituent are less well known, specifically Cp ⁄ 2 Zr = P(dmp)(PMe 3 ) from Protasiewicz and (dtbpe)Ni = P(dmp) from our laboratories [21,49].…”