Scandium, yttrium, uranium, and thorium derivatives of the 1,4-bis(trimethylsilyl)cyclo-octatetraene dianion; the X-ray crystal structure of [Sc2(η-C8H6{1,4-(SiMe3)2})2(µ-Cl)2(µ-thf)](thf = tetrahydrofuran)

Burton, Nicolas C.; Cloke, F. Geoffrey N.; Hitchcock, Peter B.; Lemos, Helen C. de; Sameh, Ausama A.

doi:10.1039/c39890001462

Cited by 65 publications

(47 citation statements)

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“…Thus, dynamic behavior of the ligand in solution is anticipated. The [15,19] In accordance with these results four signals are observed for the eight membered ring in the 13 …”

Section: Resultssupporting

confidence: 91%

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Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph₂P)₂N}⁻ ligand in the Coordination Sphere

Roesky

Gamer

Marinos

2004

Chemistry A European J

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Treatment of the recently reported potassium salt [K(thf)(n)][N(PPh(2))(2)] (n=1.25, 1.5) with anhydrous yttrium or lanthanide trichlorides in THF leads after crystallization from THF/n-pentane (1:2) to the monosubstituted diphosphanylamide complexes [LnCl(2)[(Ph(2)P)(2)N](thf)(3)] (Ln=Y, Sm, Er, Yb). The single-crystal X-ray structures of these complexes show that the metal atoms are surrounded by seven ligands in a distorted pentagonal bipyramidal arrangement, in which the chlorine atoms are located in the apical positions. The diphosphanylamide ligand is always eta(2)-coordinated through the nitrogen atom and one phosphorus atom. Further reaction of [SmCl(2)[(Ph(2)P)(2)N](thf)(3)] with K(2)C(8)H(8) or reaction of [LnI(eta(8)-C(8)H(8))(thf)(3)] with [K(thf)(n)][N(PPh(2))(2)] in THF gives the corresponding cyclooctatetraene complexes [Ln[(Ph(2)P)(2)N](eta(8)-C(8)H(8))(thf)(2)] (Ln=La, Sm). The single crystals of these compounds contain enantiomerically pure complexes. Both compounds adopt a four-legged piano-stool conformation in the solid state. The structures of the A and the C enantiomers were established by single-crystal X-ray diffraction. The more soluble bistrimethylsilyl cyclooctatetraene complex [Y[(Ph(2)P)(2)N](eta(8)-1,4-(Me(3)Si)(2)C(8)H(6))(thf)(2)] was obtained by transmetallation of Li(2)[1,4-(Me(3)Si)(2)C(8)H(6)] with anhydrous yttrium trichloride in THF followed by the addition of one equivalent of [K(thf)(n)][N(PPh(2))(2)]. The (89)Y NMR signal of the complex is split up into a triplet, supporting other observations that the phosphorus atoms are chemically equivalent in solution and, thus, dynamic behavior of the ligand in solution can be anticipated.

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“…Thus, dynamic behavior of the ligand in solution is anticipated. The [15,19] In accordance with these results four signals are observed for the eight membered ring in the 13 …”

Section: Resultssupporting

confidence: 91%

“…Elemental analyses were performed at the microanalytical laboratory of the Institute of Inorganic Chemistry at Karlsruhe. LnCl 3 , [20] (Ph 2 P) 2 NH, [21] 1,4-(Me 3 Si) 2 C 8 H 8 , [19] [SmI(C 8 H 8 )(thf) 3 ], [22] [LaI(C 8 H 8 )(thf) 3 ], [22] and [K(thf) n ][N(PPh 2 ) 2 ] (n= 1.25, 1.5) [9] were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph₂P)₂N}⁻ ligand in the Coordination Sphere

Roesky

Gamer

Marinos

2004

Chemistry A European J

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“…Closely related very bulky N,N'-disubstituted formamidinate ligands such as DippForm - [DippFormH = N,methanimidamide] have also been frequently employed in this area (Cole et al, 2007;Junk & Cole, 2007]. Another ligand system besides cyclopentadienyl, which is traditionally very important in organolanthanide chemistry, is the cyclooctatetraenyl dianion (= COT) (Edelmann, 1995) and its ring-substituted derivatives such as 1,4-bis(trimethylsilyl)cyclooctatetraenyl (= COT'') (Burton et al, 1989;Burton et al, 1993). Rare-earth metal complexes of the type (COT)Ln[RC(NR') 2 ](THF) have been reported by Schumann et al (1995).…”

Section: Methodsmentioning

confidence: 97%

“…For bulky formamidinate ligands, see: Cole et al (2007); Junk & Cole (2007). For the COT 00 ligand, see: Burton et al (1989Burton et al ( ,1993.…”

Section: Related Literaturementioning

confidence: 99%

[N,N′-Bis(2,6-diisopropylphenyl)methanimidamidato][η⁸-1,4-bis(trimethylsilyl)cyclooctatetraenyl](tetrahydrofuran)samarium(III) toluene monosolvate

et al. 2010

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The title compound, [Sm(C25H35N2)(C14H24Si2)(C4H8O)]·C7H8, was prepared by treatment of anhydrous samarium trichloride with a 1:1 mixture of in situ-prepared Li(DippForm) [DippFormH = N,N′-bis(2,6-diisopropylphenyl)methanimidamide] and Li2(COT′′) [COT′′ = 1,4-bis(trimethylsilyl)cyclooctatetraenyl] in tetrahydrofuran (THF). Despite the presence of two very bulky ligands (COT′′ and DippForm), the molecule still contains one coordinated THF ligand. The overall coordination geometry around the SmIII atom resembles a three-legged piano-stool with the COT′′ ligand being η8-coordinated and the DippForm− anion acting as an N,N′-chelating ligand [Sm—N = 2.5555 (15) and 2.4699 (15) Å]. The asymmetric unit also contains a disordered molecule of toluene, the refined ratio of the two components being 0.80 (4):0.20 (4).

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“…33 The scandium atom in 3 is located approximately 0.5 Å above the plane defined by the three nitrogen atoms (Fig. 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.…”

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

confidence: 97%

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.

262

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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Scandium, yttrium, uranium, and thorium derivatives of the 1,4-bis(trimethylsilyl)cyclo-octatetraene dianion; the X-ray crystal structure of [Sc₂(η-C₈H₆{1,4-(SiMe₃)₂})₂(µ-Cl)₂(µ-thf)](thf = tetrahydrofuran)

Cited by 65 publications

References 0 publications

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph₂P)₂N}⁻ ligand in the Coordination Sphere

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph₂P)₂N}⁻ ligand in the Coordination Sphere

[N,N′-Bis(2,6-diisopropylphenyl)methanimidamidato][η⁸-1,4-bis(trimethylsilyl)cyclooctatetraenyl](tetrahydrofuran)samarium(III) toluene monosolvate

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

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Scandium, yttrium, uranium, and thorium derivatives of the 1,4-bis(trimethylsilyl)cyclo-octatetraene dianion; the X-ray crystal structure of [Sc2(η-C8H6{1,4-(SiMe3)2})2(µ-Cl)2(µ-thf)](thf = tetrahydrofuran)

Cited by 65 publications

References 0 publications

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph2P)2N}− ligand in the Coordination Sphere

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph2P)2N}− ligand in the Coordination Sphere

[N,N′-Bis(2,6-diisopropylphenyl)methanimidamidato][η8-1,4-bis(trimethylsilyl)cyclooctatetraenyl](tetrahydrofuran)samarium(III) toluene monosolvate

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

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Scandium, yttrium, uranium, and thorium derivatives of the 1,4-bis(trimethylsilyl)cyclo-octatetraene dianion; the X-ray crystal structure of [Sc₂(η-C₈H₆{1,4-(SiMe₃)₂})₂(µ-Cl)₂(µ-thf)](thf = tetrahydrofuran)

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph₂P)₂N}⁻ ligand in the Coordination Sphere

Yttrium and Lanthanide Diphosphanylamides: Syntheses and Structures of Complexes with one {(Ph₂P)₂N}⁻ ligand in the Coordination Sphere

[N,N′-Bis(2,6-diisopropylphenyl)methanimidamidato][η⁸-1,4-bis(trimethylsilyl)cyclooctatetraenyl](tetrahydrofuran)samarium(III) toluene monosolvate