An Entry to Stable Mixed Phosphine–Osmium–NHC Polyhydrides
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https://figshare.com/articles/dataset/An_Entry_to_Stable_Mixed_Phosphine_Osmium_NHC_Polyhydrides/3219469
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资源简介：
An
entry to mixed phosphine–osmium–NHC polyhydride complexes
is described, starting from the five-coordinate hydrido–alkylidyne
compounds [OsHCl(CPh)(IPr)(PR3)]OTf (IPr = 1,3-bis(2,6-disopropylphenyl)imidazolylidene;
OTf = CF3SO3; PR3 = PiPr3 (1), PPh3 (2)). The experimental procedure involves the borylation of
the Os–C triple bond of 1 and 2 with
NaBH4 and the subsequent alcoholysis of the borylation
products OsH2Cl(η2-H-BCH2Ph)(IPr)(PR3) (PR3 = PiPr3 (3), PPh3 (4)) or OsH2(η2:η2:H2BCH2Ph)(IPr)(PiPr3) (5). Stirring of 3 in 2-propanol affords the five coordinate
chloride–trihydride OsH3Cl(IPr)(PiPr3)2 (6), which reacts
with NaBH4 to give OsH3(κ2-H2BH2)(IPr)(PiPr3) (7). This trihydride–tetrahydrideborate
derivative and its PPh3 counterpart OsH3(κ2-H2BH2)(IPr)(PPh3) (8) can be also obtained in a one-pot procedure, starting from 1 and 2 and using methanol at −60 °C
instead of 2-propanol as alcoholysis agent. The bonding situation
in 7 and 8, analyzed by DFT calculations
using AIM and NBO methods, resembles that found in B2H6 and contrasts with the bonding situation in the bis-σ-borane
derivative 5. Stirring of 7 and 8 in 2-propanol leads to the corresponding d2-hexahydride
derivatives OsH6(IPr)(PR3) (PR3 =
PiPr3 (9), PPh3 (10)), which reduce the CN triple bond
of benzonitrile and promote the subsequent chelate-assisted ortho-CH bond activation of the resulting phenylmethanimine,
to form the trihydride compounds OsH3{κ2-N,C-(NHCH-C6H4)}(IPr)(PR3)2 (PR3 =
PiPr3 (11), PPh3 (12)), containing a stabilized orthometalated
aldimine.
创建时间：
2016-05-10
