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Mixed‐Transition‐Metal Acetylides: Synthesis and Characterization of Complexes with up to Six Different Transition Metals Connected by Carbon‐Rich Bridging Units
Author(s) -
Packheiser Rico,
Ecorchard Petra,
Rüffer Tobias,
Lang Heinrich
Publication year - 2008
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200701915
Subject(s) - chemistry , transition metal , tetrahydrothiophene , ferrocene , metal , medicinal chemistry , stereochemistry , benzene , catalysis , organic chemistry , electrochemistry , electrode
The synthesis and reaction chemistry of heteromultimetallic transition‐metal complexes by linking diverse metal‐complex building blocks with multifunctional carbon‐rich alkynyl‐, benzene‐, and bipyridyl‐based bridging units is discussed. In context with this background, the preparation of [1‐{(η 2 ‐dppf)(η 5 ‐C 5 H 5 )RuCC}‐3‐{( t Bu 2 bpy)(CO) 3 ReCC}‐5‐(PPh 2 )C 6 H 3 ] ( 10 ) (dppf=1,1′‐bis(diphenylphosphino)ferrocene; t Bu 2 bpy=4,4′‐di‐ tert ‐butyl‐2,2′‐bipyridyl; Ph=phenyl) is described; this complex can react further, leading to the successful synthesis of heterometallic complexes of higher nuclearity. Heterotetrametallic transition‐metal compounds were formed when 10 was reacted with [{(η 5 ‐C 5 Me 5 )RhCl 2 } 2 ] ( 18 ), [(Et 2 S) 2 PtCl 2 ] ( 20 ) or [(tht)AuCC‐bpy] ( 24 ) (Me=methyl; Et=ethyl; tht=tetrahydrothiophene; bpy=2,2′‐bipyridyl‐5‐yl). Complexes [1‐{(η 2 ‐dppf)(η 5 ‐C 5 H 5 )RuCC}‐3‐{( t Bu 2 bpy)(CO) 3 ReCC}‐5‐{PPh 2 RhCl 2 (η 5 ‐C 5 Me 5 )}C 6 H 3 ] ( 19 ), [{1‐[(η 2 ‐dppf)(η 5 ‐C 5 H 5 )RuCC]‐3‐[( t Bu 2 bpy)(CO) 3 ReCC]‐5‐(PPh 2 )C 6 H 3 } 2 PtCl 2 ] ( 21 ), and [1‐{(η 2 ‐dppf)(η 5 ‐C 5 H 5 )RuCC}‐3‐{( t Bu 2 bpy)(CO) 3 ReCC}‐5‐{PPh 2 AuCC‐bpy}C 6 H 3 ] ( 25 ) were thereby obtained in good yield. After a prolonged time in solution, complex 25 undergoes a transmetallation reaction to produce [( t Bu 2 bpy)(CO) 3 ReCC‐bpy] ( 26 ). Moreover, the bipyridyl building block in 25 allowed the synthesis of Fe‐Ru‐Re‐Au‐Mo‐ ( 28 ) and Fe‐Ru‐Re‐Au‐Cu‐Ti‐based ( 30 ) assemblies on addition of [(nbd)Mo(CO) 4 ] ( 27 ), (nbd=1,5‐norbornadiene), or [{[Ti](μ‐σ,π‐CCSiMe 3 ) 2 }Cu(NCMe)][PF 6 ] ( 29 ) ([Ti]=(η 5 ‐C 5 H 4 SiMe 3 ) 2 Ti) to 25 . The identities of 5 , 6 , 8 , 10–12 , 14–16 , 19 , 21 , 25 , 26 , 28 , and 30 have been confirmed by elemental analysis and IR, 1 H, 13 C{ 1 H}, and 31 P{ 1 H} NMR spectroscopy. From selected samples ESI‐TOF mass spectra were measured. The solid‐state structures of 8 , 12 , 19 and 26 were additionally solved by single‐crystal X‐ray structure analysis, confirming the structural assignment made from spectroscopy.