Peripherally-metallated porphyrins: meso-η1-porphyrinyl-platinum(II) complexes of 5,15-diaryl- and 5,10,15-triarylporphyrins
Peripherally-metallated porphyrins: meso-η1-porphyrinyl-platinum(II) complexes of 5,15-diaryl- and 5,10,15-triarylporphyrins
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外围金属化卟啉：5,15-二芳基-和5,10,15-三芳基卟啉的内消旋-η1-卟啉基-铂(II)配合物
DOI：
10.1142/s1088424602000828
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发表时间：
2002
影响因子：
1.5
通讯作者：
D. Arnold
中科院分区：
文献类型：
--
作者：
R. D. Hartnell;Alison J. Edwards;D. Arnold
外围金属化的meso-η1-卟啉基铂（II）络合物如反式-[PtBr（NiDPP）（PPh 3）2]（H2 DPP = 5，15-二苯基卟啉）与有机锂试剂的尝试复分解反应由于在与金属取代基相反的卟啉环碳上的竞争性加成而失败。该反应可以通过使用5，10，15-三芳基卟啉，例如5，10，15-三苯基卟啉（H2 TrPP）和5-苯基-10，20-双（3′，5 ′-二叔丁基苯基）卟啉（H2 DAPP）作为底物来防止。这些三芳基卟啉很容易使用Senge及其同事的方法制备，通过将苯基锂加入到适当的5，15-二芳基卟啉中，然后进行水溶液质子分解和氧化。它们是方便的可溶性结构单元，用于在剩余的游离中位碳上进行选择性取代和随后的转化。Pt（0）三（膦）络合物的溴化、任选的中心金属化和氧化加成的顺序以高的总产率产生有机铂卟啉。Pt（II）中心上的溴配体可以被炔基亲核试剂（包括5-乙炔基NiDPP）取代，以形成具有第二Pt-C键的内消旋-η1-卟啉基铂（II）络合物的第一实例。卟啉铂（II）双（叔膦）配合物的范围扩展到三乙基膦类似物，通过氧化加成H2 TrPPBr的Pt（PEt 3）3，和最初形成的顺式加合物仅缓慢热转化为反式-[PtBr（H2 TrPP）（PEt 3）2]16。通过X射线晶体学测定了NiDAPP 9 b、trans-[Pt（NiDPP）（C2 NiDPP）（PPh 3）2]14和16的分子结构。
Attempted metathesis reactions of peripherally-metallated meso-η1-porphyrinylplatinum(II) complexes such as trans-[PtBr(NiDPP)(PPh3)2](H2DPP = 5,15-diphenylporphyrin) with organolithium reagents fail due to competitive addition at the porphyrin ring carbon opposite to the metal substituent. This reaction can be prevented by using 5,10,15-triarylporphyrins, e.g. 5,10,15-triphenylporphyrin (H2TrPP) and 5-phenyl-10,20-bis(3′,5′-di-t-butylphenyl)porphyrin (H2DAPP) as substrates. These triarylporphyrins are readily prepared using the method of Senge and co-workers by addition of phenyllithium to the appropriate 5,15-diarylporphyrins, followed by aqueous protolysis and oxidation. They are convenient, soluble building blocks for selective substitutions and subsequent transformations at the remaining free meso carbon. The sequence of bromination, optional central metallation and oxidative addition of Pt(0) tris(phosphine) complexes generates the organoplatinum porphyrins in high overall yields. The bromo ligand on the Pt(II) centre can be substituted by alkynyl nucleophiles, including 5-ethynyl NiDPP, to form the first examples of meso-η1-porphyrinylplatinum(II) complexes with a second Pt-C bond. The range of porphyrinylplatinum(II) bis(tertiary phosphine) complexes was extended to the triethylphosphine analogues, by oxidative addition of H2TrPPBr to Pt(PEt3)3, and the initially-formed cis adduct is only slowly thermally transformed to trans-[PtBr(H2TrPP)(PEt3)2]16. The molecular structures of NiDAPP9b, trans-[Pt(NiDPP)(C2NiDPP)(PPh3)2]14 and 16 were determined by X-ray crystallography.