An unusual Ni₂Si₂P₈cluster formed by complexation and thermolysis

Abstract

A ternary Ni2Si2P8 cluster compound is formed selectively by thermolysis of a well-defined nickel complex. This reaction illustrates a potentially useful strategy for the preparation of heteroatom-doped transition metal-phosphide clusters.

A Homoleptic Diphosphatetrahedrane Nickel(0) Complex

“…The C−C bonds of the tetrahedral moieties in complex 1 (1.471(2) to 1.474(2) Å) are only very slightly elongated compared to ( t BuCP) 2 (1.458 Å) and C (1.462(12) Å) [7] . The Ni−P bonds of 1 (2.2947(4) to 2.3082(4) Å) are somewhat longer than those for Ni complexes with a bridging μ,η 2:2 ‐P 2 moiety or a side‐on coordinated μ,η 2:2 ‐P 4 unit, e. g. 2.2354(7) to 2.2648(8) Å in [Ni 2 ( i Pr 2 Im) 4 (μ,η 2:2 ‐P 2 )], [14] 2.241(1) to 2.250(1) Å in ((μ 2 :η 2 ,η 2 ‐P 2 ){Ni(IMes)(CO)} 2 , [15] 2.255(4) to 2.277(2) Å in [( Dipp nacnac)Si(μ,η 2:2 ‐P 4 )Ni(nacnac)], [16] and 2.2657(6) to 2.2923(8) Å in [[(IPr)Ni{(μ‐η 2:2 ‐P 4 )Si( Dipp nacnac)} 2 ] ( i Pr 2 Im=1,3‐di( iso ‐propyl)imidazolin‐2‐ylidene, IMes=1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene, nacnac=CH[C(Me)N(Dipp)] 2 , Dipp nacnac=CH[C(Me)N(Dipp)][C(CH 2 )N(Dipp)], Dipp=2,6‐di‐ iso ‐propylphenyl, IPr=1,3‐bis(2,6‐di‐ iso ‐propylphenyl)imidazolin‐2‐ylidene) [17] …”

“…Dipp = 2,6-di-isopropylphenyl, IPr = 1,3-bis(2,6-di-iso-propylphenyl)imidazolin-2ylidene). [17] The Ni complex 1 was isolated in 23 % yield as an indigocolored solid. The relatively low yield can likely be attributed to the thermal instability of 1 at room temperature.…”

“…Figure 2. Solid-state molecular structure of [Ni{η 2 -(tBuCP) 2 } 3 ] (1).Displacement ellipsoids are drawn at the 50 % probability level; H-atoms have been omitted for clarity; selected bond lengths [Å] and angles [°]: Ni1À P1 2.3082(4), Ni1À P2 2.3005(4), Ni1À P3 2.2962(4), Ni1À P4 2.3035(4), Ni1À P5 2.3074(4), Ni1À P6 2.2947(4), P1À P2 2.3288(5), P3À P4 2.3319(5), P5À P6 2.3302(5), P1À C1 1.8479(14), P1À C2 1.8495(15), P2À C1 1.8477(15), P2À C2 1.8471(15), P3À C3 1.8475(16), P3À C4 1.8429(15), P4À C3 1.8496(16), P4À C4 1.8427(15), P5À C5 1.8479(16), P5À C6 1.8418(16), P6À C5 1.8473(14), P6À C6 1.8451(15), C1À C2 1.473(2), C3À C4 1.474(2), C5À C6 1.471(2); C1À P1À P2 50.94(5), C2À P1À P2 50.91(5), C1À P1À C2 46.96(7), C1À P2À P1 50.94(4), C2À P2À C1 46.99(7), C2À P2À P1 51.00(5), P2À C1À P1 78.12(6), C2À C1À P1 66.58(8), C2À C1À P2 66.48(8), P2À C2À P1 78.10(6), C1À C2À P1 66.46(8), C1À C2À P2 66.52(8), P2À Ni1À P1 60.703(14), Ni1À P1À P2 59.486(14), P3À Ni1À P1 100.002(17), P4À Ni1À P1 152.359(18), P3À Ni1À P2 101.880(16), P2À Ni1À P4 101.526(16).…”