Size-Selective Reactions of cis-Mo(CO)4{Ph2P(CH2CH2O)nCH2CH2PPh2-P,P'} (n = 4, 5) Metallacrown Ethers with Mercury(II) Salts. Crystal Structure of cis-Mo(CO)4{.mu.-Ph2P(CH2CH2O)5CH2CH2PPh2-P,P',O,O',O'',O''',O''''}.cntdot.HgCl2, an Unusual Bimetallic Complex Containing a Molecular Cleft

Gray, Gary M.; Duffey, Christina H.

doi:10.1021/om00001a037

Cited by 35 publications

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“…Metallacrown ethers are a unique class of transition-metal complexes that are formed when α,ω-bis(phosphorus donor)−polyether ligands chelate transition metals. − Metallacrown ethers that contain the conformationally mobile Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 ( 1 ) ligand exhibit a variety of phosphine coordination geometries. These geometries include cis-octahedral ( cis -Mo(CO) 4 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 2 ) 4 ), trans-octahedral ( trans -Mo(CO) 4 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 3 ) 6 and cis , cis , trans -RuCl 2 (CO) 2 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 4 ) 7 ), and cis-square planar ( cis -PtCl 2 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 5 ) 5 ).…”

Section: Introductionmentioning

confidence: 99%

“…These geometries include cis-octahedral ( cis -Mo(CO) 4 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 2 ) 4 ), trans-octahedral ( trans -Mo(CO) 4 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 3 ) 6 and cis , cis , trans -RuCl 2 (CO) 2 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 4 ) 7 ), and cis-square planar ( cis -PtCl 2 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 5 ) 5 ). Complex 2 binds alkali metal cations, methanol, and water 9 and also rapidly isomerizes into 3 in the presence of HgCl 2 . This isomerization may involve an intermediate in which the HgCl 2 coordinates to both the metallacrown ether and a carbonyl oxygen atom …”

Section: Introductionmentioning

confidence: 99%

“…Complex 2 binds alkali metal cations, methanol, and water 9 and also rapidly isomerizes into 3 in the presence of HgCl 2 . This isomerization may involve an intermediate in which the HgCl 2 coordinates to both the metallacrown ether and a carbonyl oxygen atom …”

Section: Introductionmentioning

confidence: 99%

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Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄ Ligands. X-ray Crystal Structure of cis-Mo(CO)₄{1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄-P,P‘}

1998

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A new R,ω-bis(phosphine)-polyether ligand, 1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 , has been synthesized and used to prepare a number of conformationally restrained metallacrown ethers. The reaction of 1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 and Mo(CO) 4 (nbd) gives a good yield of cis-Mo-(CO) 4 {1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 -P,P′}. This complex has been isomerized to trans-Mo-(CO) 4 {1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 -P,P′} using both UV light and HgCl 2 catalysis. The reaction of 1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 with fac-RuCl 2 (CO) 3 (THF) initially yields a mixture of monomeric and oligomeric cis,cis,trans-[RuCl 2 (CO) 2 {1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 -P,P′}] n metallacrown ethers. Surprisingly, the oligomeric metallacrown ethers slowly convert into the monomeric metallacrown ether at ambient temperature in a chloroform-d solution. This does not occur with the conformationally mobile [cis,cis,trans-RuCl 2 (CO) 2 {Ph 2 P(CH 2 CH 2 O) 4 -CH 2 CH 2 PPh 2 -P,P′}] n metallacrown ethers. The X-ray crystal structure of cis-Mo(CO) 4 {1,2-(Ph 2 P(CH 2 CH 2 O) 2 ) 2 C 6 H 4 -P,P′} has also been determined. The four ether oxygens lie in a plane, and the average cross-ring oxygen-oxygen distance is slightly larger than those in metallacrown ethers containing Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 ligands.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄ Ligands. X-ray Crystal Structure of cis-Mo(CO)₄{1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄-P,P‘}

1998

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“…Bis(imidazol-1-yl), bis(pyrazol-1-yl), and bis(benzimidazol-1-yl) polyether type compounds react with K 2 [PtCl 4 ] to yield square planar dichloro{bis(azolyl)polyether}platina(II) type complexes (1)(2)(3)(4)(5)(6)(7). In addition, L1 and L2 react with K 2 [PtI 6 ] to yield the respective diiodoplatinum(II) complexes 8 and 9 via reductive elimination.…”

Section: Discussionmentioning

confidence: 99%

“…The synthesis of several such metallacrown ethers has been described with, frequently, phosphorus or nitrogen donor moieties as the ligating units connecting the metal to the polyether backbone [2][3][4][5][6]. Furthermore, the propensity of metallacrown ethers to bind metal cations in the ring cavity has been demonstrated [1,7].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, characterization and X-ray crystal structures of polyether and ethylene bridged bis(azolyl) platinum(II) complexes

Kelly

Gómez‐Ruiz

Steinborn

et al. 2008

Transition Met Chem

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The preparation of platinum(II) complexes of the types [PtCl 2 {Y(CH 2 CH 2 O) x CH 2 CH 2 Y}] (Y: imidazol-1-yl, im; pyrazol-1-yl, pz or benzimidazol-1-yl, bim) and [PtI 2 {im(CH 2 CH 2 O) x CH 2 CH 2 im}] with varying ligand backbone length (x between 0 and 3) is described. A new bis(pyrazol-1-yl) polyether compound, pz(CH 2 CH 2 O) 2 CH 2 -CH 2 pz, is reported. Spectroscopic characterization of the complexes is discussed. Two crystal structures of the general formula [PtCl 2 {im(CH 2 CH 2 O) x CH 2 CH 2 im}] (x is 1 or 3) are also reported.Abbreviations bim Benzimidazol-1-yl im Imidazol-1-yl pz Pyrazol-1-yl

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Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

Lindner

Veigel

Ortner

et al. 2000

Eur. J. Inorg. Chem.

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The 5,5′‐bis(hydroxyalkyl)‐2,2′‐bipyridines 4a–c (Scheme 1) were prepared either in one step (4b, 4c) or in four steps (4a) starting with 5,5′‐dimethyl‐2,2′‐bipyridine in each case. Reaction of 4a–c with mesyl chloride afforded the bis(mesylates) [–C5H3N–(CH2)n–CH2–OSO2Me]2 5a–c [n = 1 (a), 2 (b), 3 (c)], which could easily be transformed into the diphosphanes 6a–c by reaction with LiPPh2. Treatment of 6c, 6b with Cl2Pt(NCPh)2 and (RC6H4)2Pt(COD) according to the high‐dilution method resulted in the formation of the tetraphosphadiplatinacyclophanes [–C5H3N–(CH2)4–PPh2PtCl2PPh2–(CH2)4–C5H3N–]2 (7c) and [–C5H3N–(CH2)3–PPh2Pt(C6H4R)2PPh2–(CH2)3–C5H3N–]2 (8b, 9b) (8b: R = H, 9b: R = tBu), respectively (Scheme 2). The molecular structures of 8b and 9b were elucidated by X‐ray structural analyses. The noncoordinated bipyridine moieties in 8b were employed to encapsulate copper(I) to give the host/guest complex 10b (Scheme 3), which was investigated by FAB‐MS, NMR spectroscopy, and cyclovoltammetry. 10b exhibited a quasi‐reversible oxidation at E1/2 = –0.31 V and an electrodeposition‐redissolution redox system at E1/2 = –0.79 V, owing to the formation of copper at the surface of the working electrode.

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Size-Selective Reactions of cis-Mo(CO)4{Ph2P(CH2CH2O)nCH2CH2PPh2-P,P'} (n = 4, 5) Metallacrown Ethers with Mercury(II) Salts. Crystal Structure of cis-Mo(CO)4{.mu.-Ph2P(CH2CH2O)5CH2CH2PPh2-P,P',O,O',O'',O''',O''''}.cntdot.HgCl2, an Unusual Bimetallic Complex Containing a Molecular Cleft

Cited by 35 publications

References 0 publications

Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄ Ligands. X-ray Crystal Structure of cis-Mo(CO)₄{1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄-P,P‘}

Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄ Ligands. X-ray Crystal Structure of cis-Mo(CO)₄{1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄-P,P‘}

Synthesis, characterization and X-ray crystal structures of polyether and ethylene bridged bis(azolyl) platinum(II) complexes

Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

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Size-Selective Reactions of cis-Mo(CO)4{Ph2P(CH2CH2O)nCH2CH2PPh2-P,P'} (n = 4, 5) Metallacrown Ethers with Mercury(II) Salts. Crystal Structure of cis-Mo(CO)4{.mu.-Ph2P(CH2CH2O)5CH2CH2PPh2-P,P',O,O',O'',O''',O''''}.cntdot.HgCl2, an Unusual Bimetallic Complex Containing a Molecular Cleft

Cited by 35 publications

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Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph2P(CH2CH2O)2)2C6H4 Ligands. X-ray Crystal Structure of cis-Mo(CO)4{1,2-(Ph2P(CH2CH2O)2)2C6H4-P,P‘}

Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph2P(CH2CH2O)2)2C6H4 Ligands. X-ray Crystal Structure of cis-Mo(CO)4{1,2-(Ph2P(CH2CH2O)2)2C6H4-P,P‘}

Synthesis, characterization and X-ray crystal structures of polyether and ethylene bridged bis(azolyl) platinum(II) complexes

Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

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Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄ Ligands. X-ray Crystal Structure of cis-Mo(CO)₄{1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄-P,P‘}

Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄ Ligands. X-ray Crystal Structure of cis-Mo(CO)₄{1,2-(Ph₂P(CH₂CH₂O)₂)₂C₆H₄-P,P‘}