Borazin—metallkomplexe : VI. Über ligandenaustauschreaktionen an borazin—metallkomplexen: synthese von B-trimethylborazin-tricarbonylchrom

Me₃B₃N₃H₃Cr(CO)₃ has been obtained by ring-ligand exchange starting from Et₃B₃N₃Me₃Cr(CO)₃ and Me₃B₃N₃H₃. The new compound has been characterised by means of their IR, NMR, UV and mass spectroscopic data.     

Si-Containing Amides of Phosphoric Acid

The first representative of the N-silylmethylamides of phosphoric acid O=P[NMe(CH₂SiMe _n (OEt)_3-n ]₃ have been synthesized by interaction of MeNHCH₂SiMe _n (OEt)_3-n (n = 2, 3) with POCl₃. The interaction of the N,N′,N″-trimethyl-N,N′,N″-tris[(ethoxydimethyl- silyl)methyl]triamide phosphoric acid with BF₃·Et₂O or BCl₃ results in the formation of the N,N′,N″-trimethyl-N,N′,N″-tris[(fluorodimethyl-silyl)methyl]triamide phosphoric acid or N,N′,N″-trimethyl-N,N′,N″-tris[(chlorodimethylsilyl)methyl]triamide phosphoric acid. NMR data show on the tetracoordinate state of silicon in these products.     

A quantum chemical study of Cr(CO)3(B3N3H6 ? n F n ) (n = 1–3) complexes

The electronic structure and properties of Cr(CO)₃(B₃N₃H_{6 ? n} F _n ) (n = 1?C3) complexes have been explored using hybrid density functional B3LYP theory. Calculations indicate B-fluorinated isomers are more stable, and less polarizable, than N-fluorinated isomers. The aromatic natures of the borazine rings have been analyzed by nucleus independent chemical shift (NICS). The atoms in molecules (AIM) analysis indicates that Cr-C and Cr-N bonds distance is well correlated with the electron density of critical point (??_cp) in all species.     

Synthesis and spectroscopic studies of homo- and heteroleptic N-arylsalicylaldiminates of titanium(IV), zirconium(IV) and chromium(III)

Homo- and heteroleptic N-arylsalicylaldiminate derivatives of Ti^IV and Zr^IV of the type, MX_4–x (OC₆H₄CH=NAr) _x (X = OPrⁱ, x = 2,3; X = Cl, x = 1,2,3,4; Ar = C₆H₃Me₂-2,6, C₆H₃Et₂-2,6) have been prepared by reactions in the desired molar ratios of: (i) Ti(OPrⁱ)₄/Zr(OPrⁱ)₄·PrⁱOH with N-arylsalicylaldimines in benzene, and (ii) MCl₄ (M = Ti, Zr) with Me₃SiOC₆H₄CH=NAr or HOC₆H₄CH=NAr in the presence of Et₃N as a base or the potassium salt of N-arylsalicylaldimines in benzene. The three homoleptic derivatives of Cr^III, Cr(OC₆H₄CH=NAr)₃ (Ar = C₆H₂Me₃-2,4,6, C₆H₃Et₂-2,6, C₆H₃Prⁱ ₂-2,6) have also been prepared by salt-elimination. All of these new derivatives have been characterized by elemental analyses, spectroscopic [i.r., ¹H and ¹³C-n.m.r. (Ti and Zr complexes), and electronic (for Cr complexes)] studies, as well as molecular weight measurements.     

Si-Containing Amides of Phosphoric Acid

Summary. The first representative of the N-silylmethylamides of phosphoric acid O=P[NMe(CH₂SiMe _n (OEt)_3-n ]₃ have been synthesized by interaction of MeNHCH₂SiMe _n (OEt)_3-n (n = 2, 3) with POCl₃. The interaction of the N,N′,N″-trimethyl-N,N′,N″-tris[(ethoxydimethyl- silyl)methyl]triamide phosphoric acid with BF₃·Et₂O or BCl₃ results in the formation of the N,N′,N″-trimethyl-N,N′,N″-tris[(fluorodimethyl-silyl)methyl]triamide phosphoric acid or N,N′,N″-trimethyl-N,N′,N″-tris[(chlorodimethylsilyl)methyl]triamide phosphoric acid. NMR data show on the tetracoordinate state of silicon in these products. Professor Vadim Aleksandrovich Pestunovich, our chief, teacher and friend died on July 4^th, 2004     

Cationic arenechromium-nitrosyls and -hydrides

Complexes Cr(CO)₂L(C₆Me_6-nH_n), n = 0-3, L = CO and PPh₃, react with NOPF₆ in methanol/toluene to give [Cr(CO)L(NO)(C₆Me_6-nH_n)] PF₆, n = 0-3, L = CO; n = 0, L = PPh₃, and these react with nucleophiles (X^-) to give cyclohexadienyl derivatives Cr(CO)₂(NO)(C₆Me_6-nH_nX); the compounds Cr(CO)₂(PhCCPh)(C₆Me_6-nH_n) react with NOPF₆ to yield [Cr(H)(CO)₂(PhCCPh)(C₆Me_6-nH_n)] PF₆, n = 0 and 1.     

Preparation of complexes formed in the reaction between diironnanocarbonyl and tetraalkyl(phenyl)diphosphine disulfides,R2P(S)P(S)R2 (R=Et,n -Pr,n -Bu,Ph)

Fe₂(CO)₉ and R₂P(S)P(S)R₂ (R = Et, n-Pr, n-Bu, Ph) react to form two types of cluster complexes Fe₃(CO)₉(μ₃-S)₂ (1), Fe₂(CO)₆(μ-SPR₂)₂ (2A)–(2D), [2A, R = Et; 2B, R = n-Pr; 2C, R = n-Bu; 2D, R = Ph]. The complexes result from phosphorus–phosphorus bond scission; in the former sulfur abstraction has also occurred. The complexes have been characterized by elemental analyses, FT-IR and ³¹P-[¹H]-NMR spectroscopy and mass spectrometry.     

Synthesis and spectroscopic characterization of bis(N-alkyldithiocarbamato)nickel(II) complexes: crystal structures of [Ni(S2CNH(n-Pr))2] and [Ni(S2CNH(i-Pr))2]

Bis(N-alkyldithiocarbamato)nickel(II) complexes (1–5) [Ni(S₂CNHR)₂] (where R?=?Me, Et, n-Pr, i-Pr, n-Bu) were synthesized by the reaction of NiCl₂?·?6H₂O and the corresponding sodium salt of N-alkyldithiocarbamate in 1?:?2 molar ratio in aqueous medium. These bis(N-alkyldithiocarbamato)nickel(II) complexes (1–5) were characterized by elemental analysis, UV-Visible, IR, and ¹H/¹³C-NMR spectroscopy. The crystallographic investigation of [Ni(S₂CNH(n-Pr))₂] (3) and [Ni(S₂CNH(i-Pr))₂] (4) revealed distorted square-planar geometry around nickel(II). The dithiocarbamates have anisobidentate coordination with nickel and the dithiocarbamates are trans.     

Mass spectrometry of organic compounds in the group V elements—I: Straight chain aliphatic derivatives

Comparative investigations of the mass spectra of eEH₂, Me₂EH, Et₂EH(E = N, P); Me₃E, Et₃E(E = N, P, As, Sb, Bi). (n-Pr)₃E(E = Sb, Bi); (n-Bu)₃E(E = P, As); (n-C₅H₁₁)₃As and (n-C₆H₁₃)₃As as well as Et₂AsBr have been carried out. Deuteroanalogues, metastable transitions and low voltage spectra were used for elucidation of the fragmentation paths. The mass spectra of MeN(CH₂)₂ and CD₃N(CH₂)₂ were studied to analyse the structure of the fragments. The main degradation path of amines, i.e. α-cleavage, was shown to be untypical for P, As, Sb and Bi derivatives.     

Use of Neodymium Diiodide in the Synthesis of Organosilicon, ‐Germanium and ‐Tin Compounds

The reactivity of neodymium diiodide, NdI₂ ( 1 ), towards organosilicon, ‐germanium and ‐tin halides has been investigated. Compound 1 readily reacts with Me₃SiCl in DME to give trimethylsilane (6 %), hexamethyldisilane (4 %) and (Me₃Si)₂O (19 %). The reaction with Et₃SiBr in THF results in formation of Et₃SiSiEt₃ (17 %) and Et₃SiOBuⁿ (34 %). Alkylation of Me₃SiCl with PrⁿCl in the presence of 1 in THF affords Me₃SiPrⁿ (10 %), Me₃SiOBuⁿ (52 %) and Me₃SiSiMe₃ (1 %). The main product identified in the reaction mixture formed upon interaction of 1 with dichlorodimethylsilane Me₂SiCl₂ in THF is di‐n‐butoxydimethylsilane Me₂Si(OBuⁿ)₂ (54 %) together with minor amounts of Me₂Si(OBuⁿ)Cl. The reaction of 1 with Me₃GeBr under the same conditions produces Me₃GeGeMe₃ (44 %), Me₃GeH (3 %), and Me₃GeI (7 %). An analogous set of products was obtained in the reaction with Et₃GeBr. Treatment of trimethyltin chloride with 1 causes reduction of the former to tin metal (74 %). Me₃SnH (7 %) and hexamethyldistannane (11 %) were identified in the volatile products. The reaction of 1 with Me₃SiI provides straightforward access to hepta‐coordinated NdI₃(THF)₄ ( 2 ), the structure of which was determined by X‐ray diffraction.     

Producing highly linear polyethylenes by using t‐butyl‐functionalized 2,6‐bis(imino)pyridylchromium(III) chlorides

A new family of t‐butyl substituted chromium(III) chloride complexes ( Cr1 – Cr6 ), bearing 2‐(1‐(2,6‐dibenzhydryl‐4‐t‐butylphenylimino)ethyl)‐6‐(1‐(arylimino)ethyl)pyridine (aryl = 2,6‐Me₂C₆H₃ Cr1 , 2,6‐Et₂C₆H₃ Cr2 , 2,6‐i‐Pr₂C₆H₃ Cr3 , 2,4,6‐Me₃C₆H₂ Cr4 and 2,6‐Et₂‐4‐MeC₆H₂ Cr5 ) or 2,6‐bis(1‐(2,6‐dibenzhydryl‐4‐t‐butylphenylimino)ethyl)pyridine ( Cr6 ), has been synthesized by the reaction of CrCl₃·6H₂O in good yield with the corresponding ligands ( L1 – L6 ), respectively. The molecular structures of Cr2 and Cr6 were characterized by X‐ray diffraction highlighted a distorted octahedral geometry with the coordinated N,N,N ligand and three bonded chlorides around the metal center. On activation with modified methylaluminoxane or triisobutyl aluminum, most of the chromium precatalysts exhibit good activities toward ethylene polymerization and produce linear polyethylenes with high‐molecular weight. In addition, an in‐depth catalytic evaluation of Cr2 was conducted to investigate how cocatalyst type and amount, reaction temperature, and run time affect the catalytic activities and polymer properties. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 1049–1058     

Komplexchemie at P-reicher Phosphane und Silylphosphane. VI. Bildung und Struktur der Chromcarbonylkomplexe des Tris(trimethylsilyl) heptaphosphanortricyclans (Me3Si)3P7

Formation and Structures of Chromium Carbonyl Complexes of Tris(trimethylsily)heptanortricyclane (Me₃Si)₃P₇ (Me₃Si)₃P₇ 1 reacts with one equivalent of Cr(Co)₅THF 2 to give the yellow (Me₃Si)₃P₇[Cr(Co)₅] 4. The Cr(Co)₅group is attached to a P^e atom. Yellow (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 is obtained either from reacting 1 with two equivalents of 2 , or from 4 with one equivalent of 2. One Cr(CO)₅ groups in 5 is coordinated to a P^e atom, the other one to a P,^b atom. Similarly, Yellow (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 results from reacting 5 with one equivalent of 2 . Two Cr(CO)₅ groups in 6 are linked to P^b atoms, and the third one either to a P^e or the P^a atom (assignment not completely clear). Derivatives containing a P^e bridge appear in reactions of 1 with higher amounts of 2 . Such, 5 forms mixtures of the red compounds (Me₃Si)₃P₇ × [Cr(CO)₅]₂[Cr(CO)₄] 8 and (Me₃Si)₃P₇[Cr(CO)₅] × [Cr(CO)₄] 9 , and even preferably 9 with four equivalents of 2 . In 8 , one Cr(CO)₅ group is attached to that p^e atom which is not engaged in the Cr(CO)₄ bridge, and the second to one of the P^b atoms directly adjacent to the bridge. The additional Cr(CO)₅ group in 9 is coordinated to the remaining P^b atom directly adjacent to the bridge. In reactions of 5 with even higher amounts of 2 , four Cr(CO)₅ groups and one Cr(CO)₄ bridge attach to the basic P₇ skeleton to from the less stable Me₃P₇[Cr(CO)₅]₄[Cr(CO)₄]. (Me₃Si)₃P₇ 1 reacts considerably slower with Cr(CO)₅THF 2 than R₃P₇ (R = Et, iPr). Cr(CO)₄NBD 3 reacts with 1 , but it was not possible to isolate (Me₃Si)₃P₇[Cr(CO)₄]. However, 4 with 3 forms (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 , and 5 with 3 yields (Me₃Si)₃P₇[Cr(CO)₅]₂[Cr(CO)₄] 8 . The structures of 4 , 5 , 7 , 8 or 9 are quite analogous to those of the derivatives of Et₃P₇ but there exist significant differences in stability and reactivity. While Et₃P₇[Cr(CO)₅]₂ in solution rearranges to give the stable Et₃P₇[Cr(CO)₅][Cr(CO)₄], the analogous (Me₃Si)₃P₇[Cr(CO)₅][Cr(CO)₄] 7 is not stable and is not obtained from (Me₃Si)₃P₇[Cr(CO)₅]₂ 5 . Et₃P₇[Cr(CO)5]₃ can just be detected spectroscopically and rearranges easily to give Et₃P₇[Cr(CO)₅]₂ [Cr(CO)₄] whereas (Me₃Si)₃P₇[Cr(CO)₅]₃ 6 can be isolated. These differences are caused by the greater steric requirements of Me₃Si groups. The formation of a P^e–Cr(CO)₄–P^e bridge, e.g., requires a Me₃Si group in 1 to switch from the s to the as position. Whereas many of the complex compounds of R₃P₇ (R = Et, iPr) crystallize easily, the analogous derivatives of (Me₃Si)₃P₇ did not yield crystals. The structures of the products were assigned by evaluating the coordination shift in their ₃₁P NMR spectra and by comparision of these spectra with those of such derivatives of Et₃P₇ which previously had been investigated by single crystal structure determinations.     

Beiträge zur Chemie des Phosphors. 159. Über die Reaktion des Diphosphaborirans (t-BuP)2BN(i-Pr)2 mit Kalium bzw. Kaliumnaphthalid

Contributions to the Chemistry of Phosphorus. 159. On the Reaction of the Diphosphaborirane (t-BuP)₂BN(i-Pr)₂ with Potassium or Potassium Naphthalenide The reaction of (t-BuP)₂BN(i-Pr)₂ with potassium or K-naphthalenide in tetrahydrofuran leads to K(t-Bu)P? ;BN(i-Pr)₂? P(t-Bu)K ( 1 ) via P? ;P bond cleavage of the three-membered ring skeleton. Above ? 78°C 1 changes into the asymmetric compound K(t-Bu)P? ;P(t-Bu)? BHN(i-Pr)₂ ( 2 ). In dimethoxyethane additionally the monometallated diphosphaborirane K(t-Bu)P₂BN(i-Pr)₂ ( 3 ) is formed. 1 and 3 , which could be isolated free from other phosphorus containing compounds, as well as the corresponding silylphosphanes Me₃Si(t-Bu)P? ;BN(i-Pr)₂? ;P(t-Bu)SiMe ₃ ( 4 ) and Me₃Si(t-Bu)P₂BN(i-Pr)₂ ( 5 ) were characterized by NMR spectroscopy. Protolysis of 3 or 5 leads to a decomposition of the three-membered ring skeleton with formation of H(t-Bu)P? ;PH₂.     

Komplexchemie P-reicher Phosphane und Silylphosphane. VIII. Zur unterschiedlichen Tendenz der Bildung von Chromcarbonyl-Komplexen silylierter-alkylierter Phosphane und Diphosphane

Transition Metal Complexes of P-rich Phosphanes and Silylphosphanes. VIII. Concerning the Different Tendencies of Silylated and Alkylated Phosphanes and Diphosphanes to Form Chromium Carbonyl Complexes The influence of the substituents Me₃Si tBu and Me in phosphanes and diphosphanes on the formation of complex compounds with Cr(CO)₅THF is investigated. tBu(Me₃Si)P? P(SiMe₃)₂ 1 and (tBu)₂P? P(SiMe₃)₂ 2, resp., react with Cr(CO)₅THF 4 at ?18°C by coordinating Cr(CO)₅ to the P(SiMe₃)₂ group to give tBu(Me₃Si)P? P^IV(SiMe₃), · Cr(CO)₅ 1 a, tBu(Me₃Si)P^IV? P^IV(SiMe₃)₂ · Cr(CO)₄ 1b and (tBu)₂P? P^IV(SiMe₃)₂ · Cr(CO)₅ 2a . In the reaction of 1 with 4 using a molar ratio of 1:2 at first 1 a is formed which reacts on to yield completely 1 b. In a mixture of the dissolved compounds (Me₃Si)₃P 5, (tBu)₃P 6 and (tBu)₃P? P(SiMe₃)₂ 2 only 5 and 6 react with Cr(CO)₅THF yielding (Me₃Si)₃P · Cr(CO)₅ and (tBu)₃P · Cr(CO)₅, but 2 does not yet react. In a solution of (Me₃Si)₃P 5, P₂Me₄ 7 and (Me₃Si)₂P? PMe₂ 3 only 5 and 7 react with Cr(CO)₅THF (0.25 to 1.5 equivalents with respect to 3) to give (Me₃Si)₃P · Cr(CO)₅, P₂Me₄ · Cr(CO)₅ and P₂Me₄ · 2Cr(CO)₅. The formation of complexes with Cr(CO)₅THF of the phosphanes 5 and 6 is clearly favoured as compared to the silylated diphosphanes 2 and 3 (not to P₂Me₄); the PR₂ groups (R = tBu, Me in 2 or 3 ) don't have a strong influence.     

Synthesis and characterization of chromocenes containing bulky cyclopentadienyl ligands

Two equivalents of K[Cp′] (Cp′=C₅(i-Pr)₃H₂, C₅(i-Pr)₄H, C₅(t-Bu)₂H₃) react with CrCl₂ in THF to give the corresponding chromocenes, Cp′₂Cr, in good yield. Despite the presence of bulky substituents on the rings that could affect their properties, the complexes are extremely air- and moisture-sensitive, and possess a low-spin ground state. The low-spin paramagnetic nature of each chromocene was confirmed by magnetic susceptibility measurements. The solid-state structure of [C₅(i-Pr)₃H₂]₂Cr was obtained using single crystal X-ray analysis. It displays rigorously parallel rings, with an average Cr–C(ring) distance of 2.17(1)Å; the chromium resides on a crystallographically imposed inversion center. The orientation of the isopropyl groups minimizes unfavorable steric interactions between the rings.     

Synthesis and desilylation of some bis(trimethylsilyl)alkenes and polymers bearing bis(silyl)alkenyl groups

The synthesis of various vinylbis(silanes) from some aryl and heteroaryl aldehydes and (Me₃Si)₃CLi in Et₂O is described. Friedel-Crafts reaction of 1,1-bis(trimethylsilyl)-2-(2-naphthyl)ethene with various acyl chlorides (RCOCl, R = Me, Et, i-Pr, i-Bu, n-pent) gave the corresponding α-silyl-α,β-unsaturated enones with high E steroselectivity. Moreover, poly(styrene)-co-[2,2-bis(trimethylsilyl)ethenyl(styrene)] obtained via the reaction of polymers bearing pendant enone functions and (Me₃Si)₃CLi, reacts with the same acyl chlorides in the presence of catalytic amount of AlCl₃ to give the new macromolecules bearing α-silyl-α,β-unsaturated enones and α,β-unsaturated enones.     

Synthesis of Differently Substituted N- and P-Aminodiphosphinoamine PNPN-H Ligands

Abstract

On the basis of the known aminodiphosphinoamine ligand Ph₂PN(i-Pr)P(Ph) N(i-Pr)-H (3a), differently substituted aminodiphosphinoamine PNPN-H ligands (3) were prepared. By using different synthetic methods, the N-substituted ligands Ph₂PN (i-Pr)P(Ph)N(c-Hex)-H (3b), Ph₂PN(c-Hex)P(Ph)N(i-Pr)-H (3g), and Ph₂PN(i-Pr)P(Ph) N[(CH₂)₃Si(OEt)₃]-H (3c), in addition to the formerly described Ph₂PN(n-Hex)P (Ph)N (i-Pr)-H (3h), Ph₂PN(i-Pr)P(Ph)N(Et)-H (3d), Ph₂PN(i-Pr)P(Ph)N(Me)-H (3e), and Ph₂PN(c-Hex)P(Ph)N(c-Hex)-H (3f), were obtained. In addition, Ph₂PN(i-Pr)P(Me)N(i-Pr)-H (3i), (cyclopentyl)₂PN(i-Pr)P(Ph)N(i-Pr)-H (3j), (-O-CH₂-CH₂-O-)PN(i-Pr)P(Ph)N(i-Pr)-H (3k), and (1-Ad)₂PN(i-Pr)P(Ph)N(i-Pr)-H (3l) were prepared with different P-substitutions. All compounds were characterized and the molecular structures of the intermediates Ph₂PN(i-Pr)P(Ph)Cl (1a) and (cyclopentyl)₂PN(i-Pr)P(Ph)Cl (1e) and the ligand (1-Ad)₂PN(i-Pr)P(Ph)N(i-Pr)-H (3l) were investigated by single-crystal X-ray diffraction.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Reactions of Distibanes with [Fe2(CO)9]: Synthesis,Structure and DFT Calculations of [(Et2Sb)4Fe4(CO)14], [(nPr2Sb)4Fe3(CO)10], [{(Me3SiCH2)2Sb}4Fe2(CO)6], and [2‐(Me2NCH2)C6H4SbFe2(CO)8]

The iron complexes [(Et₂Sb)₄Fe₄(CO)₁₄] ( 1 ), [(nPr₂Sb)₄Fe₃(CO)₁₀] ( 2 ), [{(Me₃SiCH₂)₂Sb}₄Fe₂(CO)₆] ( 3 ), and [2‐(Me₂NCH₂)C₆H₄SbFe₂(CO)₈] ( 4 ) were prepared by reactions of distibanes with Fe₂(CO)₉. Compounds 1 – 4 were characterized by X‐ray diffraction, ¹H NMR and IR spectroscopy as well as mass spectrometry; complex 1 was additionally characterized by density functional calculations.     

Reactions of bis(trimethylsilyl)amine and -amide with MoOCl4

Oxo-Mo(VI) imido-chloride, [MoOCl₂(NH)(Et ₂O)] _n and nitrido-chloride, [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n have been synthesized by equimolar reactions of MoOCl₄ with HN(SiMe ₃)₂ and LiN(SiMe ₃)₂, respectively. Higher molar reactions of HN(SiMe ₃)₂ lead to imido-silylamido derivatives, [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , whereas those of LiN(SiMe ₃)₂ give silylimido bridged compounds, Mo₄O₄Cl₄(NSiMe ₃)₆ and Mo₄O₄(NSiMe ₃)₈. Elemental analyses, redox titration, magnetic moment, molecular weight, molar conductance, infrared,¹H-NMR and TG-DTG-DTA studies are reported.

---

Reaktionen von Bis(trimethylsilyl)amin und -amid mit MoOCl₄

Zusammenfassung Durch equimolare Reaktionen von MoOCl₄ mit HN(SiMe ₃)₂ und LiN(SiMe ₃)₂ wurden die Oxo-Mo(VI) Imido-chloride [MoOCl₂(NH)(Et ₂O)] _n und die Nitrido-chloride [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n dargestellt. Höhermolekulare Reaktionen von HN(SiMe ₃)₂ führen zu Imido-silylamido Derivaten [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , währenddessen die von LiN(SiMe ₃)₂ silylimidoüberbrückte Verbindungen ergeben: Mo₄O₄Cl₄(NSiMe ₃)₆ und Mo₄O₄(NSiMe ₃)₈. Die Strukturen sind mit Elementaranalysen, Redoxtitrationen, Messung der magnetischen Momente, Molekulargewichten, molarer Leitfähigkeit, Infrarot,¹H-NMR und TG-DTG-DTA-Untersuchungen charakterisiert.

     

Ethynylisopropylgermanes and Their Trimethylsilyl Derivatives

The reaction of ethynylmagnesium bromide with chloroisopropylgermanes (i-Pr_{4 - n} GeCl_{/sub> n} , n = 1-3) was used to prepare previously unknown ethynylisopropylgermanes i-Pr_{4 - n} Ge(CCH) _n (n = 1-3). The reaction of Me₃SiCCMgBr with i-PrGeCl₃ afforded i-Pr(Me₃SiCC)_{3 - n} GeCl _n (n = 1, 2). The reaction of the monochloride with BrMdCCH gave i-Pr(HCC)₂GeCCSiMe₃, while with the dichloride, i-Pr(HCC)·Ge(CSiMe₃)₂ formed. The latter compounds were obtained by independent synthesis from i-PrGe(CCH)₃, EtMgBr, and ClSiMe₃. The reaction of (bromomagnesioethynyl)triisopropylgermane with Me₃SiCl gave i-Pr₃GeCSiMe₃.