Syntheses and structure of dimeric yttrium tris [bis(trimethylsilyl) phosphanide]; X-ray structures of [(thf)LiCl·(thf)2LiPtBu2]2 and Y[CH(SiMe3)2]3

Westerhausen, Matthias; Hartmann, M.; Schwarz, W.

doi:10.1016/s0020-1693(97)05776-9

Cited by 47 publications

(19 citation statements)

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“…20 The trimethylsilyl ligands coordinate trigonal pyramidally to the Y atom (Y-C ) 236 pm). An attempt to prepare a mixed alkyl alkoxide with the less bulky CH 2 SiMe 3 ligand led to isolation of the ion pair [(Me 3 SiCH 2 ) x -(Me 3 CO) 1-x Y(OCMe 3 ) 4 (Li(THF)) 4 Cl][Y(CH 2 SiMe 3 ) 4 ].…”

Section: Homoleptic σ-Alkyl Complexesmentioning

confidence: 99%

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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Over the years one major challenge has remained in organolanthanide chemistry: the synthesis of homoleptic alkyl and aryl complexes. The simplest organometallic compounds of the rare earths are the species LnR 2 or LnR 3 with the rare earth metals in their common oxidation states Ln 2+ and Ln 3+ which imply the coordination of only two or three ligands to the metal center. This is usually insufficient to meet the lanthanides' demands of steric saturation through high coordination numbers.Hence for a long time, only indirect evidence could be found for the existence of simple homoleptic organolanthanide compounds; the isolation and characterization of compounds belonging to this class were first achieved recently using pentafluorophenyl for Ln 2+ derivatives 12 and very bulky alkyl ligands for Ln 3+ species. [13][14][15] Especially for alkyls, very little structural data are available for compounds without any trimethylsilyl-substituted ligands which generally ensure higher stability. But nevertheless, due to the difficulties of their synthesis and their high reactivity alkyls and aryls still represent an interesting class of compounds. 16 Homoleptic σ-Alkyl ComplexesShortly after the synthesis of the first divalent solvent-free Ln alkyl, [(Me 3 Si) 3 C] 2 Yb, 17 the Eu analogue was prepared similarly by the reaction of EuI 2 and KC(SiMe 3 ) 3 in benzene. 18 It also features the bent structure displayed by the Yb complex but with a slightly smaller C-Eu-C angle (C-Eu-C ) 136°, C-Yb-C ) 137°) and longer Eu-C bonds (Eu-C ) 261 pm, Yb-C ) 249/250 pm). Salt metathesis was then again applied successfully to synthesize the first divalent Sm alkyl, Sm[C(SiMe 3 ) 2 (SiMe 2 OMe)] 2 (THF) Frank T. Edelmann was born in Hamburg, Germany, in 1954. He studied chemistry from 1974 to 1979 at the University of Hamburg, where he obtained his Diplom in 1979 and doctoral degree in 1983. His Ph.D. thesis entitled "The chemistry of the tricarbonyl(fulvene) chromium complexes" was carried out under the supervision of Prof. Ulrich Behrens. This was followed by two years (1983−1985) of postdoctoral research as a Feodor Lynen Fellow of the Alexander-von-Humboldt Foundation in the groups of Professors Josef Takats (

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Section: Homoleptic σ-Alkyl Complexesmentioning

confidence: 99%

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

2002

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“…The reasons for lack of well-characterized yttrium phosphanides include extreme sensitivity towards moisture and air, side reactions during the synthesis as well as unintelligible preparative procedures. Schumann and Frisch [11] published the synthesis of [(thf) 2 Y(PtBu 2 ) 3 ] via the metathesis reaction of yttrium(III) halide with lithium phosphanide, however, we were unable to isolate pure and defined yttrium phosphanides from this procedure [10]. In Table 1 an overview on structurally characterized yttrium phosphanides is given.…”

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“…Coordination compounds of s-block metals exhibit mainly heteropolar M-P bonds (Lewis acid-base interactions between the cation and the phosphanide anion), whereas compounds of isoelectronic Sc and Y often show unusual coordination spheres. Examples include molecules such as M[E(SiMe 3 ) 2 ] 3 (M = Sc: E = N [8]; M = Y: E = N [9], CH [10]) which contain three-coordinate metal atoms in trigonal pyramidal environments. Investigations on molecular yttrium phosphanide complexes are rather rare and there are only very few examples of isolated and structurally characterized yttrium phosphanides.…”

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Synthesis and crystal structure of dinuclear [(thf)3YCl2{μ-P(H)C6H2-2,4,6-Me3}]2 with seven-coordinate yttrium atoms

Krieck

Görls

Westerhausen

2009

Inorganic Chemistry Communications

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The metalation of HP(SiMe 3 ) 2 with Y[CH(SiMe 3 ) 2 ] 3 gives the homoleptic {Y[P(SiMe 3 ) 2 ] 3 } 2 (1) which crystallizes from toluene in the monoclinic space group P2 1 /c. Die Metallierung von Bis(trimethylsilyl)phosphan mit Yttrium-tris[bis(trimethylsilyl)methanid] ergibt nahezu quantitativ extrem luft-und feuchtigkeitsempfindliches Yttrium-tris[bis(trimethylsilyl)phosphanid] (1) [6]. The metathesis reaction of [1,3-(Me 3 Si) 2 C 5 H 3 ] 2 YCl with KPSitBu 3 yields (tetrahydrofuran-O)-1,1Ј,3,3Ј-tetrakis(trimethylsi-Es gibt nur wenige Berichte über molekulare Phosphanide des Yttriums, die außerdem oft nur unzureichend charakterisiert sind.

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Synthese und Strukturen von Yttrium-tris[bis(trimethylsilyl)phosphanid] und 1, 1', 3, 3'-Tetrakis(trimethylsilyl)yttrocen-tri(tert-butyl)silylphosphanid

Westerhausen

Schneiderbauer

Hartmann

et al. 2002

Z. anorg. allg. Chem.

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The metalation of HP(SiMe 3 ) 2 with Y[CH(SiMe 3 ) 2 ] 3 gives the homoleptic {Y[P(SiMe 3 ) 2 ] 3 } 2 (1) which crystallizes from toluene in the monoclinic space group P2 1 /c. The yttrium atoms are in a distorted tetrahedral environment with Y-P bond lengths of 267.7 and 284.8 pm to the terminal and bridging substituents, respectively. The metathesis reaction of [1,3-(Me 3 Si) 2 C 5 H 3 ] 2 YCl with KPSitBu 3 yields (tetrahydrofuran-O)-1,1Ј,3,3Ј-tetrakis(trimethylsi-Es gibt nur wenige Berichte über molekulare Phosphanide des Yttriums, die außerdem oft nur unzureichend charakterisiert sind. Bei diesen aus der Literatur bekannten Vertretern handelt es sich um. Strukturelle Daten lagen bisher für keines dieser Yttriumphosphanide vor. Auch in der Festkörperchemie ist die Zahl der Verbindungen mit Y-P-Bindungen außerordentlich begrenzt [7]. Für die Synthese der Yttriumphosphanide stehen zwei Synthesewege zur Verfügung. Dabei treten bei der Metathesereaktion eines Yttriumhalogenids mit einem Alkalimetallphosphanid Probleme auf, die durch die Metallierung des Phosphans mit Trialkylyttrium umgangen werden können. Die Metallierung von Bis(trimethylsilyl)phosphan mit Yttrium-tris[bis(trimethylsilyl)methanid] ergibt nahezu quantitativ extrem luft-und feuchtigkeitsempfindliches Yttrium-tris[bis(trimethylsilyl)phosphanid] (1) [6]. Das dimere Vorliegen dieser Verbindung konnte bereits früher aus NMR-Daten abgeleitet werden [δ(P b ) ϭ Ϫ107.8, δ(P t ) ϭ Ϫ104.8, 1 J(Y,P b ) ϭ 56.7 Hz, 1 J(Y,P t ) ϭ 122.4 Hz, 2 J(P,P) ϭ 5.0 Hz], während uns jetzt die Bestimmung der Molekülstruktur gelang. Die Yttriumatome sind verzerrt tetraedrisch von je zwei verbrückenden und zwei terminalen Phosphanid-Liganden umgeben. Die Molekülstruktur dieses homoleptischen Yttrium-trisphosphanids 1 ist in Abb. 1 dargestellt, die Strukturdaten sind in Tabelle 1 zusammengefasst. Die Y-P-Bindungslängen zu den terminalen (Mittelwert: 267.7 pm) und verbrückend auftretenden (Mittelwert: 284.8 pm) Phosphanid-Liganden unterscheiden sich um 17 pm. Die größere Koordina-lyl)yttrocene-tri(tert-butyl)silylphosphanide (2). The molecular structure of 2 in solution was deduced by NMR spectroscopy and X-ray crystallography. The coupling constants 1 J(Y,P) and 1 J(P,H) show values of 144.0 Hz and 201.0 Hz, respectively.

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Syntheses and structure of dimeric yttrium tris [bis(trimethylsilyl) phosphanide]; X-ray structures of [(thf)LiCl·(thf)2LiPtBu2]2 and Y[CH(SiMe3)2]3

Cited by 47 publications

References 72 publications

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes

Synthesis and crystal structure of dinuclear [(thf)3YCl2{μ-P(H)C6H2-2,4,6-Me3}]2 with seven-coordinate yttrium atoms

Synthese und Strukturen von Yttrium-tris[bis(trimethylsilyl)phosphanid] und 1, 1', 3, 3'-Tetrakis(trimethylsilyl)yttrocen-tri(tert-butyl)silylphosphanid

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