Interaction of Allylic Alcohols with Halogeno-bridged Platinum(II) Complexes (X = Cl or Br) and n4>2: Crystal Structure of

DOI: 10.1039/DT9800000064

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 64 - 69 (1980)

Update date:2022-08-05

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Authors:

Briggs, John R.

Crocker, Christopher

McDonald, Walter S.

Shaw, Bernard L.

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Article abstract of DOI:10.1039/DT9800000064

A series of comlexes of type cis- (PR3=PMe3, PEt3, PPrⁿ3, or PMe2Ph; Q=prop-2-en-1-ol, but-1-en-3-ol, or 3-methylbut-1-en-3-ol) have been prepared.The crystal structure of cis- is described: no intramolecular hydrogen bond is present.Crystal data: space group P2₁/n, a=12.540(3), b=10.668(7), c=10.929(2) Angstroem, β = 97.02(2) deg, and Z=4.The complexes cis- have been studied by variable-temperature 1H and 31P n.m.r. spectroscopy.There is no evidence for rotamers, as found with other olefin complexes.At room temperature slow dissociation to give the bridged complex and the free allyl alcohol occurs.The complex cis- does not exchange rapidly with free allyl alcohol and separate resonances due to free and complexed allyl alcohol could be observed: in contrast n4> exchanges rapidly with free allyl alcohol on the n.m.r. time scale.N.m.r. studies of the interaction between chloro-bridged complexes of the type > and allylic alcohols show that at low temperatures the bridged species is rapidly and reversibly converted into trans-1R²OH)> together with some of the O-bonded species, trans-.Above ca. 260 K the resonances start to broaden due to exchange with the bridged complex and have also become much less intense due to reversion back to the bridged complex: cis-1R²OH)> is also gradually formed above ca. 260 K.A -CH2=CHCH2OH system also shows the presence of trans- and in this case the cis isomer forms to a detectable extent even at 213 K.The bridged complex nBu^t2)2> containing the bulky phosphine shows the presence of rotamers at 243 K and with allyl alcohol two rotamers trans-nBu^t2)(CH2=CHCH2OH)> form at 213K.The 1H and 31P n.m.r. and i.r. data are given and discussed.

Full text of DOI:10.1039/DT9800000064

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