Intermolecular hydrogen bonding in isostructural pincer complexes [OH-(t-BuPOCOPt-Bu)MCl] (M = Pd and Pt)

In the crystal structure of the isostructural title compounds, namely {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridopalladium(II), [Pd(C22H39O3P2)Cl], 1, and {2,6-bis[(di-tert-butylphosphanyl)oxy]-4-hydroxyphenyl}chloridoplatinum(II), [Pt(C22H39O3P2)Cl], 2, the metal centres are coordinated in a distorted square-planar fashion by the POCOP pincer fragment and the chloride ligand. Both complexes form strong hydrogen-bonded chain structures through an interaction of the OH group in the 4-position of the aromatic POCOP backbone with the halide ligand

Crystal structure of bis(pentamethylcyclopentadienyl)(1-tert- butylisocyanido)-2-trimethylsilyl-3-[(trimethylsilyl)ethynyl]-hafnacyclopropene, (C10H15)2(C5H9N) Hf(C10H18Si2)

C35H57HfNSi2, monoclinic, P121/c1 (no. 14), a = 10.7410(3) Å, b = 16.2302(5) Å, c = 21.6945(7) Å, β = 104.512(2)°, V = 3661.3 Å3, Z = 4, R gt(F) = 0.049, wRref(F2) = 0.138, T = 200 K. © 2014 Oldenbourg Wissenschaftsverlag, München

Crystal structure of rac-[1, 2-ethylene-bis(η5-4, 5, 6, 7-tetrahydroindenyl)]1-hafna-4, 5-bis(trimethylsilyl)furan-3-one- tris(pentafluorophenyl)borane, (C20H24)Hf(Me 3SiC2SiMe3CO2)B(C6F 5)3

C47H42BF15HfO2Si2, monoclinic, P121/n1 (no. 14), a = 15.7496(4) Å = 20.4074(5) Å= 16.3115(5) Å, β = 96.313(2)°, V= 5210.9 Å3, Z = 4, Rgt(F) = 0.027, WRref(F 2) = 0.049, T= 200 K. © by Oldenbourg Wissenschaftsverlag

Crystal structure of 1, 1-bis(pentamethylcyclopentadienyl)-4, 5-bis(trimethyIsilyl)-1-hafnafuran-3-one, Hf(C10H15) 2(Me3SiC2SiMe3CO2)

C29H48HfO2Si2, orthorhombic, Pnma (no. 62), a = 16.8546(4) Å= 14.4139(6) Å= 12.1421(3) Å, V= 2949.8 Å3, Z = 4, Rgt(F) = 0.020, WR ref(F2) = 0.041, T= 200 K. © by Oldenbourg Wissenschaftsverlag

Crystal structure of μ-oxo-bis(σ- 1,2-bis(trimethylsilyl) vinylhafnocene) benzene solvate, [C2H{Si(CH3) 3}2Hf(C5H5)2] 2O ·C6H6

C42H64Hf2OSi4, monoclinic, P121/c1 (no. 14), a = 11.442(1) Å = 9.7998(6) Å, c = 19.827(2) Å, β = 95.229(7)°, V = 2213.9 Å, Z = 2, R gt(F) = 0.017, wRref(F2)=0.037, T=200K. © by Oldenbourg Wissenschaftsverlag,

{N,N-Bis[bis(2,2,2-trifluoroethoxy)phosphanyl]methylamine- κ2 P,P′}bis(η5-cyclopentadienyl) titanium(II)

The title compound, [Ti(C5H5)2(C 9H11F12NO4P2)], is a four-membered titanacycle obtained from the reaction of Cp2Ti(η 2-Me3SiC2SiMe3) and CH 3N[P(OCH2CF3)2]2 {N,N-bis[bis(trifluoroethoxy)phosphanyl]methylamine, tfepma}. The Ti II atom is coordinated by two cyclopentadienyl (Cp) ligands and the chelating tfepma ligand in a strongly distorted tetrahedral geometry. The molecule is located on a mirror plane

Crystal structure of 3,3-bis(tert-butyl-cyclopentadienyl)-bicyclo[3.1.0] hex-3-zircona-1(5)-ene-6-nickela-6,6-bis(triphenylphosphine), (C 9H13)2(ZrC4H4)Ni(C 18H15P)2

C58H60NiP2Zr, monoclinic, P12 1/n1 (no. 14), a = 12.378(3) Å = 10.353(2) Å, c = 38.031(8) Å, β = 95.74(3)°, V= 4849.2 Å, Z = 4, R gt(F) = 0.023, wRref(F2) = 0.054, T = 200 K. © by Oldenbourg Wissenschaftsverlag

Vanadium (β-(Dimethylamino)ethyl)cyclopentadienyl Complexes with Diphenylacetylene Ligands

Reduction of the V(III) (β-(dimethylamino)ethyl)cyclopentadienyl dichloride complex [η5:η1-C5H4(CH2)2NMe2]VCl2(PMe3) with 1 equiv of Na/Hg yielded the V(II) dimer {[η5:η1-C5H4(CH2)2NMe2]V(µ-Cl)}2 (2). This compound reacted with diphenylacetylene in THF to give the V(II) alkyne adduct [η5:η1-C5H4(CH2)2NMe2]VCl(η2-PhC≡CPh). Further reduction of 2 with Mg in the presence of diphenylacetylene resulted in oxidative coupling of two diphenylacetylene groups to yield the diamagnetic, formally V(V), bent metallacyclopentatriene complex [η5:η1-C5H4(CH2)2NMe2]V(C4Ph4).

Metal Hydrides Form Halogen Bonds: Measurement of Energetics of Binding

The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η5-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η5-cyclopentadienyl) is demonstrated by 1H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = −10.9 ± 0.4 and −11.8 ± 0.3 kJ/mol; ΔS° = −38 ± 2 and −34 ± 2 J/(mol·K), respectively) and found to be stronger than those for 1 with the hydrogen-bond donor indole (ΔH° = −7.3 ± 0.1 kJ/mol, ΔS° = −24 ± 1 J/(mol·K)). For the more reactive complexes 2–5, measurements are limited to determination of their low-temperature (212 K) association constants with C6F5I as 2.9 ± 0.2, 2.5 ± 0.1, <1.5, and 12.5 ± 0.3 M–1, respectively