Single-Boron Complexes of N-Confused and N-Fused Porphyrins
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- 作者：Anna M
//pubs.acs.org/images/entities/lstrok.gif" border="0">odzianowska ; Lechos
- 刊名：Inorganic Chemistry
- 出版年：2007
- 出版时间：August 20, 2007
- 年：2007
- 卷：46
- 期：17
- 页码：6950 - 6957
- 全文大小：255K
- 年卷期：v.46,no.17(August 20, 2007)
- ISSN：1520-510X
文摘
Boron(III) has been inserted into N-confused porphyrin, (NCPH)H2 (1), and N-fused porphyrin, (NFP)H (2). Thereaction of dichlorophenylborane and 1 yields 
gifchars/sigma.gif" BORDER=0 >-phenylboron N-confused porphyrin (4). The boron atom is boundby two pyrrolic nitrogen atoms and the gifchars/sigma.gif" BORDER=0 >-phenyl ligand. The N-confused pyrrole ring is not involved in the directcoordination because the C(21)-H fragment remains intact. A reaction between PhBCl2 and N-fused porphyrinproduces gifchars/sigma.gif" BORDER=0 >-phenylboron N-fused porphyrin (3+). 4 converts quantitatively into 3+ under protonation. In gifchars/sigma.gif" BORDER=0 >-phenylboronN-fused porphyrin [(NFP)BPh]Cl, the coordinating environment of boron(III) resembles a distorted trigonal pyramid,with the nitrogen atoms occupying equatorial positions and with the phenyl ligand lying at the unique apex. Boron(III)is displaced by 0.547(4) Å from the N3 plane. The B-N distances are as follows: B-N(22), 1.559(4) Å; B-N(23),1.552(4) Å; B-N(24), 1.568(4) Å; B-CipsoPh, 1.621(4) Å. 3+ can be classified as a boronium cation considering afilled octet and a complete coordination sphere. 3+ is susceptible to alkoxylation at the inner C(9) carbon atom,yielding 5-OR. The addition of acid results in protonation of the alkoxy group and elimination of alcohol, restoringthe original 3+. Density functional theory has been applied to model the molecular and electronic structure of 4,3+, and syn and anti isomers of methoxy adducts 5-OMe.
gifchars/sigma.gif" BORDER=0 >-phenylboron N-confused porphyrin (4). The boron atom is boundby two pyrrolic nitrogen atoms and the gifchars/sigma.gif" BORDER=0 >-phenyl ligand. The N-confused pyrrole ring is not involved in the directcoordination because the C(21)-H fragment remains intact. A reaction between PhBCl2 and N-fused porphyrinproduces gifchars/sigma.gif" BORDER=0 >-phenylboron N-fused porphyrin (3+). 4 converts quantitatively into 3+ under protonation. In gifchars/sigma.gif" BORDER=0 >-phenylboronN-fused porphyrin [(NFP)BPh]Cl, the coordinating environment of boron(III) resembles a distorted trigonal pyramid,with the nitrogen atoms occupying equatorial positions and with the phenyl ligand lying at the unique apex. Boron(III)is displaced by 0.547(4) Å from the N3 plane. The B-N distances are as follows: B-N(22), 1.559(4) Å; B-N(23),1.552(4) Å; B-N(24), 1.568(4) Å; B-CipsoPh, 1.621(4) Å. 3+ can be classified as a boronium cation considering afilled octet and a complete coordination sphere. 3+ is susceptible to alkoxylation at the inner C(9) carbon atom,yielding 5-OR. The addition of acid results in protonation of the alkoxy group and elimination of alcohol, restoringthe original 3+. Density functional theory has been applied to model the molecular and electronic structure of 4,3+, and syn and anti isomers of methoxy adducts 5-OMe.