Preparation, characterization, and reactivity of scandium octaethylporphyrin complexes. X-ray crystal structures of (OEP)ScCH3, (OEP)ScCH(SiMe3)2, (OEP)Sc(.eta.5-C9H7), and [(OEP)Sc]2(.mu.-OH)2

Arnold, John; Hoffman, Caroline G.; Dawson, Denisha Y.; Hollander, Frederick J.

doi:10.1021/om00033a042

Cited by 74 publications

(45 citation statements)

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“…Most metalloporphyrins having triflate as a counteranion have been obtained from (P)MCl x complexes and silver triflate or trimethylsilyltriflate [10,11,17,18]. Thus we initially attempted to prepare (P)BiX, where X Br À or Cl À , and then exchange the halide counterion with the triflate anion.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO₃CF₃)

Michaudet

Fasseur

Guilard

et al. 2000

J. Porphyrins Phthalocyanines

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The metalation of several free base porphyrins by the bismuth salts Bi(NO3)3 and Bi(SO3CF3)3 in DMF or pyridine is described. The resulting stable Bi(III) porphyrin complexes are characterized by electrochemistry, 1H NMR and UV-vis spectroscopy. The structure of ( OEP ) Bi ( SO 3 CF 3) was also determined by single-crystal X-ray diffraction and shows that ( OEP ) Bi ( SO 3 CF 3) exists as a dimer which is stabilized by electrostatic interactions in which the two [(OEP)Bi]+ cations are linked via oxygen atoms of two symmetrically related [Formula: see text] anions, leading to a heptacoordinated bismuth center. Electrochemical oxidation of ( OEP ) Bi ( SO 3 CF 3) and ( T p TP ) Bi ( SO3CF3 ) shows that only the porphyrin macrocycles are oxidized.

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Section: Resultsmentioning

confidence: 99%

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO₃CF₃)

Michaudet

Fasseur

Guilard

et al. 2000

J. Porphyrins Phthalocyanines

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“…Fryzuk and co-workers pioneered the use of multidentate amidophosphine ligands, which combine soft phosphine and hard amide donors, and incorporated such motifs into the coordination sphere of group 3 metals, including the tridentate [N(SiMe2CH2P i Pr2)2] -(P2N) in (P2N)ScR2 (R = Me, Et, CH2SiMe3) (Fryzuk et al, 1996), tetradentate (PhP[CH2(SiMe2)N(SiMe2)CH2]2PPh) 2-(P2N2) in (P2N2)Y[CH(SiMe3)2] (Fryzuk et al, 1997), and, recently, the tetradentate fc(NP i Pr2)2 in [(fc(NP i Pr2)2)Sc(THF)(-H)]2 (Halcovitch and Fryzuk, 2013). J. Arnold popularized porphyrins as supporting ligands for scandium organometallic complexes (Arnold and Hoffman, 1990;Arnold et al, 1993), and, recently, synthesized lanthanum and terbium corrole complexes (Buckley et al, 2013). Several groups reported on the use of mono-and bis-amidinate rare earth complexes as analogues of Cp*2M (Duchateau et al, 1993;Hagadorn and Arnold, 1996;Wedler et al, 1990).…”

Section: General Remarks About the Organometallic Chemistry Of Rare Ementioning

confidence: 99%

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Huang

Diaconescu

2014

Including Actinides

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Rare earth chemistry has witnessed remarkable advances in recent years. In particular, ancillary ligands other than cyclopentadienyl derivatives have been introduced to the organometallic chemistry and their complexes exhibit distinct reactivity and properties compared to the metallocene or half-sandwiched analogues. The present chapter reviews arene-bridged rare earth complexes with an emphasis on those compounds obtained by reduction reactions. A particular emphasis is placed on rare earth complexes supported by 1,1′-ferrocenediyl diamides since they show the most diverse chemistry with arenes: fused arenes, such as naphthalene and anthracene, formed inverse-sandwiched complexes, in which the arene is dianionic; weakly conjugated arenes, such as biphenyl, p-terphenyl, and 1,3,5-triphenylbenzene, were unexpectedly reduced by four electrons and led to 6-carbon, 10- electron aromatic systems; on the contrary, (E)-stilbene, which has a carbon-carbon double bond between the two phenyl rings, could only be reduced by two electrons, which were located on the carbon-carbon double bond instead of the phenyl rings.

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“…2, distance δ) and participates in almost uniform N᎐Sc᎐N angles and strongly varying O᎐Sc᎐N angles ( 36 The Sc᎐N bond distances found in porphyrin (por) derivatives of type Sc(por)L [L = Me, CH(SiMe 3 ) 2 , C 5 H 5 or C 9 H 7 ] range from 2.142(6) to 2.197(3) Å. 37 Despite there being no spectroscopic indication of any Sc ؒ ؒ ؒ (Si᎐H) interaction, the solidstate structure of 3 reveals one close Sc ؒ ؒ ؒ Si contact 34 The tendentiously widened Si᎐N᎐Si angles average 124.5(1)Њ and thus are also in agreement with a more ionic Sc᎐N bond in 3 compared to that in [Sc{N- 34 In addition, the disorder of two methyl groups of one SiHMe 2 fragment hints at a steric unsaturation of the metal centre.…”

Section: Structural Chemistry Of [Ln{n(sihme 2 ) 2 } 3 (Thf) X ]mentioning

confidence: 99%

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

Anwander

Runte

Eppinger

et al. 1998

J. Chem. Soc., Dalton Trans.

261

227

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Rare-earth silylamides of type [Ln{N(SiHMe 2 ) 2 } 3 (thf) x ] (Ln = Sc, Y, La, Nd, Er or Lu) have been prepared in high yield by reaction of 2.9 equivalents of Li[N(SiHMe 2 ) 2 ] with [LnCl 3 (thf) x ] in n-hexane or thf, depending on the solubility of the rare-earth halide precursor. The complexes [Ln{N(SiHMe 2 ) 2 } 3 (thf) 2 ] (Ln = Y, La to Lu) are isostructural in the solid state, adopting the preferred (3 ϩ 2, distorted) trigonal bipyramidal geometry, whilst [Sc{N(SiHMe 2 ) 2 } 3 (thf)] has a distorted tetrahedral co-ordination geometry and short Sc ؒ ؒ ؒ Si contacts in the solid state. The reaction of [Y{N(SiHMe 2 ) 2 } 3 (thf) 2 ] with varying amounts of AlMe 3 resulted in desolvation and alkylation with formation of AlMe 3 (thf), {AlMe 2 [µ-N(SiHMe 2 ] 2 } 2 and heterobimetallic (Y/Al) species. The generation of surface-bonded '(᎐ ᎐ ᎐ SiO) x Y[N(SiHMe 2 ) 2 ] y ' and '᎐ ᎐ ᎐ SiOSiHMe 2 ' moieties via the grafting of [Y{N(SiHMe 2 ) 2 } 3 (thf) 2 ] onto the mesoporous silicate MCM-41 is described in detail. Consideration is given to the factors governing the siloxide formation and silylation reactions, and the thermal stability of the surface species.Rare-earth amides, and in particular silylamides, 1 are of potential relevance in catalysis 2 and the material sciences. 3 Furthermore, the synthetic versatility of the Ln᎐N(SiMe 3 ) 2 moiety is well established in amine elimination reactions known as the silylamide route (Scheme 1). 1,4 Rare-earth amides are also capable of alkylation reactions via Lewis acid-base derived heterobimetallic species. 5,6 Advantages of the Ln᎐N(SiMe 3 ) 2 -based silylamide route are (i) facile availability of mono-and heterobi-metallic amide precursors, (ii) favourable (mild) reaction conditions including non-co-ordinating solvents, ambient temperature, smooth work-up procedures and 'quantitative' yield, (iii) avoidance of halide contamination and (iv) donor ligand-free products due to the weak donor capability of the released silylamine. 1 Complexes [Ln{N(SiHMe 2 ) 2 } 3 (thf) 2 ] derived from the sterically less bulky bis(dimethylsilyl)-amide ligand were introduced better to cope with the steric requirements of catalytically relevant, bulky and chelating ancillary ligands such as salen or linked cyclopentadienyl derivatives. 7 We report here a detailed synthetic and structural examination of these versatile synthetic building blocks. In addition, AlMe 3 -directed desolvation and alkylation reactions are discussed.Very recently, we found that many features of the homogeneously performed silylamide route can be transferred to a heterogeneous medium (Scheme 1). 8 Such a supramolecular approach allowed the grafting of rare-earth silylamide complexes onto a mesoporous aluminosilicate of type MCM-41 9,10 via surface organometallic chemistry. 11 The presence of 'Si᎐H' as a spectroscopic probe helped to unravel the chemical anchoring of the silylamides which proceeds via siloxide formation and silylation reactions. In this work more light will be shed on the surface organometallic chem...

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Preparation, characterization, and reactivity of scandium octaethylporphyrin complexes. X-ray crystal structures of (OEP)ScCH3, (OEP)ScCH(SiMe3)2, (OEP)Sc(.eta.5-C9H7), and [(OEP)Sc]2(.mu.-OH)2

Cited by 74 publications

References 0 publications

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO₃CF₃)

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO₃CF₃)

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

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Preparation, characterization, and reactivity of scandium octaethylporphyrin complexes. X-ray crystal structures of (OEP)ScCH3, (OEP)ScCH(SiMe3)2, (OEP)Sc(.eta.5-C9H7), and [(OEP)Sc]2(.mu.-OH)2

Cited by 74 publications

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Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO3CF3)

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO3CF3)

Rare Earth Arene-Bridged Complexes Obtained by Reduction of Organometallic Precursors

Synthesis and structural characterisation of rare-earth bis(dimethylsilyl)amides and their surface organometallic chemistry on mesoporous MCM-41 †

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Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO₃CF₃)

Synthesis, characterization and electrochemistry of bismuth porphyrins: X-ray crystal structure of (OEP)Bi(SO₃CF₃)