title: Porphyrin complexes containing coordinated BOB groups: synthesis, chemical reactivity and the structure of [BOB(tpClpp)]2+.
abstract: The reactions of boron halides with free base porphyrins under conditions where partial hydrolysis of the boron halides can occur give diboron porphyrin complexes containing BOB moieties in which each boron is bonded to two porphyrin nitrogen atoms. BF(3).OEt(2) with H(2)(por) gives B(2)OF(2)(por) (por = tpp, ttp, tpClpp, oep) which has an asymmetric structure in which one boron lies in the porphyrin plane (B(ip)) while the other lies above it (B(oop)). BCl(3).MeCN with H(2)(por) gives B(2)O(2)(BCl(3))(2)(por) which contains a four-membered B(2)O(2) ring and is stable only in the presence of excess BCl(3). BBr(3) with Li(2)(tpClpp) gives the dicationic complex [B(2)O(tpClpp)](2+) as its [BBr(4)](-) salt, and is the first example of a boron porphyrin containing three-coordinate boron to be structurally characterised. B(2)O(2)(BCl(3))(2)(por) can be chromatographed on basic alumina to give the hydroxyboron complex B(2)O(OH)(2)(por), which is deduced from its NMR spectra and DFT calculations to have a structure analogous to B(2)OF(2)(por). The OH protons are shifted upfield to near delta -4 (B(oop)-OH) and -10 (B(ip)-OH) by the diamagnetic porphyrin ring current. The reaction of either B(2)O(2)(BCl(3))(2)(por) or B(2)O(OH)(2)(por) (por = ttp, tpClpp) with alcohols (ROH, R = Et, 4-C(6)H(4)CH(3)) gives B(2)O(OR)(2)(por), which can in turn be converted to B(2)O(OR)(OH)(por) by repeated chromatography. The reaction of PhBCl(2) with H(2)(por) (por = ttp, tpClpp) gives B(2)O(Ph)(OH)(por) which has been characterised by spectroscopy in concert with DFT calculations. It is a further example of the B(2)OF(2)(por) structural type, in which the phenyl group is coordinated to the out-of-plane boron and the OH group to the in-plane boron, as are its derivatives B(2)O(Ph)(X)(tpClpp) (X = F, OEt). Steric drivers for the facile hydrolysis of haloboron porphyrins relative to their dipyrromethene and expanded porphyrin counterparts are discussed.
authors.affiliation: School of Environmental and Life Sciences, The University of Newcastle, University Drive, Callaghan, NSW 2308, Australia.
authors.forename: Warwick J
authors.initials: WJ
authors.lastname: Belcher
authors.forename: Michael C
authors.initials: MC
authors.lastname: Hodgson
authors.forename: Kenji
authors.initials: K
authors.lastname: Sumida
authors.forename: Ana
authors.initials: A
authors.lastname: Torvisco
authors.forename: Karin
authors.initials: K
authors.lastname: Ruhlandt-Senge
authors.forename: D C
authors.initials: DC
authors.lastname: Ware
authors.forename: P D W
authors.initials: PD
authors.lastname: Boyd
authors.forename: P J
authors.initials: PJ
authors.lastname: Brothers
mesh_terms: D001880:Boranes / Q000737:chemistry; D001896:Boron Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D002712:Chlorides / Q000737:chemistry; D006868:Hydrolysis; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D001880:Boranes; D001896:Boron Compounds; D002712:Chlorides; D011166:Porphyrins; C021274:boron trifluoride; C092267:boron trichloride