Carbidoheptarhenate Cluster Complexes of Cadmium and Zinc Units:  The Structure of [PPh₄]₂[Re₇C(CO)₂₁(μ₃-ZnCl)]

Abstract

Combining [PPh4]3[Re7C(CO)21] with excess MCl2 (M = Cd, Zn) in acetone provides the complexes [PPh4]2[Re7C(CO)21(MCl)] (M = Cd, 1; M = Zn, 2) in >70% yields. The crystal structure of [PPh4]2[Re7C(CO)21(μ3-ZnCl)] shows a typical carbidoheptarhenate complex, with the zinc center positioned symmetrically over one Re3 face (average Re−Zn distance = 2.71 Å).

Heterobimetallic Complexes of Rhenium and Zinc: Potential Catalysts for Homogeneous Syngas Conversion

“…Initially formed in approximately 80% yield by NMR, the formyl species slowly decomposes over several days to give a red solution, which by NMR contains some regenerated 1 as well as a new species exhibiting a downfield 31 P NMR shift (47.8 ppm), suggesting that P may be part of a five-membered ring. This compound was found by X-ray crystallography to have structure 11 (Scheme ), a rare example (only the second structurally characterized) of an organometallic complex containing a Re–Zn bond (Figure ). The Re–Zn bond length of 2.61977(15) Å is about 0.07 Å shorter than those in [PPh 4 ] 2 [Re 7 C(CO) 21 ZnCl] .…”

A Trimetallic Compound Containing Zn−Zr Bonds: Cp2Zr(ZnR)2 (Cp = C5H5; R = C6H3-2,6-(2,4,6-i-Pr3C6H2)2)

“…Indeed, the Zn−Zr−Zn core represents a rare symmetric Zn−M−Zn type of Zn−M (M = transition metal) bonding. Another reported example of this structural type is the Zn−Co−Zn linkage in (CpZn) 2 Co(Cp)PPh 3 , while most examples contain either symmetric M−Zn−M or unsymmetrical M−Zn metallic cores. ,,− The 99.12(3)° Zn−Zr−Zn bond angle of 3 is similar to the 100.39(4)° Ga−Zr−Ga angle of Cp 2 Zr(GaR) 2 ( 5 ), the 95.06(4)° Sn−Zr−Sn angle of Cp 2 Zr(SnR 2 ) 2 (R = CH(SiMe 3 ) 2 ) ( 6 ), and the In−Zr−In angle (95.37(2)°) for Cp 2 Zr(InR) 2 ( 7 ) 3 but is significantly greater than the 87.70(3)° Ga−Zr−Ga angle in Cp 2 Zr{Ga[N(Ar)C(H)] 2 } 2 ][Li(THF) 4 ] (Ar = C 6 H 3 Pr i 2 -2,6) and especially the 74.90(2)° Zn−Co−Zn angle of (CpZn) 2 Co(Cp)PPh 3 3 Molecular structure of 3 (thermal ellipsoids are shown at the 30% probability level).…”

“…Furthermore, what would be the nature of such Zn−M bonding? Although compounds containing zinc−transition-metal (mostly groups 6−8) bonds have been known for some time, − compounds containing Zn−M (M = group 4: Ti, Zr, Hf) bonds have not been reported. We now report the synthesis and molecular structure of Cp 2 Zr(ZnR) 2 ( 3 ; R = C 6 H 3 -2,6-(2,4,6- i -Pr 3 C 6 H 2 ) 2 ), the first structurally characterized compound containing a Zn−Zr bond.…”

“…Furthermore, what would be the nature of such Zn-M bonding? Although compounds containing zinc-transition-metal (mostly groups 6-8) bonds have been known for some time, [9][10][11][12][13][14] compounds containing Zn-M (M ) group 4: Ti, Zr, Hf) bonds have not been reported. We now report the synthesis and molecular structure of Cp 2 Zr(ZnR) 2 (…”

Heterotetrametallic Re–Zn–Zn–Re Complex Generated by an Anionic Rhenium(I) β-Diketiminate

“…The Re–Zn distances in 4 are 2.4681(3) and 2.4711(3) Å, which are substantially shorter (by ca. 0.15 Å) than the two other crystallographically characterized examples of Re–Zn interactions. , …”