Dihydrogen with Frequency of Motion Near the¹H Larmor Frequency. Solid-State Structures and Solution NMR Spectroscopy of Osmium Complexestrans-[Os(H··H)X(PPh₂CH₂CH₂PPh₂)₂]⁺(X = Cl, Br)

Abstract

A high-yield route to the new complexes OsBr2(dppe)2 and trans-OsHBr(dppe)2 starting from (NH4)2[OsBr6] is described. The new 5-coordinate complexes [OsX(dppe)2]PF6 (X = Cl (8Os) and X = Br (9Os)) are prepared by reaction of cis-OsX2(dppe)2 with NaPF6. Complexes 8Os and 9Os consist of distorted trigonal bipyramidal cations with “Y”-shaped equatorial planes. They react in CH2Cl2 with H2 or HD (1 atm) to give complexes trans-[Os(H··H)X(dppe)2]PF6 (X = Cl (1OsPF6), X = Br (2OsPF6)) or trans-[Os(H··D)X(dppe)2]PF6, respectively. The last complexes have J(H,D) = 13.9 and 13.7 Hz, respectively. The BF4 - salts of these complexes, 1OsBF4 and 2OsBF4, respectively, are prepared by reacting trans-OsHX(dppe)2 with HBF4·Et2O or DBF4·Et2O. These complexes are characterized by NMR, IR, and FAB MS. The single-crystal X-ray and neutron diffraction studies of 1OsPF6 revealed an elongated H··H ligand with d HH = 1.11(6) (X-ray) or 1.22(3) Å (neutron) occupying one site in an octahedral complex. The X-ray diffraction study of 2OsBF4 produced a similar structure with d HH = 1.13(8) Å. One fluorine of the anion in each structure is positioned near the acidic H2 ligand. A linear relationship between d HH and J(H,D) for many dihydrogen complexes is used to indicate that complexes 1Os and 2Os have H−H distances of about 1.2 Å in solution. Plots of ln(T 1) versus inverse temperature for 1Os and 2Os are distorted from the usual “V” shape, suggesting that the rotational frequency of the H2 ligand is near that of the Larmor frequency. Therefore the d HH for 1Os is between the values of 1.04 and 1.31 Å calculated from the T 1(min) for fast and slow spinning H2, respectively. The chloride ligand in trans-[Os(H··H)Cl(L)2]+ buffers the effect of changing the cis ligands L from dppe to depe to dcpe so that there is little change in the H−H distance. Complexes 1Os and 2Os have pK a values of 7.4 and 5.4, respectively, while trans-[Os(H2)H(dppe)2]+ is much less acidic with a pK a of 13.6. These pK a values and some E 1/2 values are used to show that 1Os and 2Os are dihydride-like even though they have relatively short H−H distances. Properties of trans-[Os(H··H)Cl(depe)2]BF4 (3Os) are also reported.

The Influence of N‐Heterocyclic Carbenes (NHC) on the Reactivity of [Ru(NHC)4H]+ With H2, N2, CO and O2

“…[25,26] This is in good agreement with the value of 0.90 calculated using the formula for a fast spinning dihydrogen ligand on the basis of the T 1 A C H T U N G T R E N N U N G (min) value of 22 ms determined at 226 K (400 MHz). [27] Although the molecular structure of 7 was characterised by X-ray crystallography (Figure 6), neither the h 2 -H 2 ligand nor the ruthenium hydride could be reliably located.…”

The Activation of Dihydrogen

“…The g 2 -H 2 ligand is also capable of forming intermolecular H-bonds. Morris and coworkers have noted that one of the fluorine atoms of the BF 4 or PF 6 counterions is consistently oriented toward the g 2 -H 2 ligand in the solid-state structures of a series of cationic g 2 -H 2 complexes [115,116].…”

Bis[1,2-bis(diphenylphosphino)ethane-P,P']chloroosmium(II) Hexafluorophosphate Dichloromethane Solvate

“…The X-ray and neutron diffraction studies of (3) are discussed elsewhere (Maltby et al, 1996). An X-ray study of the five-coordinate compound…”