The intramolecularly phosphorus stabilized element-13 organyls Me2M(CH2)(3)P(t-Bu)(2) (M = Al (1), Ga (2), In (3)) and C12M(CH2)(3)P(t-Bu)(2) (M = Al (5), Ga (6)) are formed by reacting Me2MCl and MCl3 with t-Bu2P(CH2)(3)MgCl and t-Bu2P(CH2)(3)Li (4), respectively The reaction of Et2PCH2C6H4Br-2 (7) with BuLi and Me2InCl produces Me2InC6H4CH2PEt2-2 (8). [Me2InCH2PMe2](2) (9) results from the reaction of Me2PCH2Li with Me2InCl. The successive addition of BuLi, Cl(CH2)(3)Br, and Me2AlCl to t-BuPH2 does not lead to the expected Me2Al(CH2)(3)PH(t-Bu) (10), but af-fords [{cyclo-P(t-Bu)(CH2)(3)}CO2](AlMe2Cl)(2) (12) formed during work-up in the presence of CO,. The new compounds were characterized by elemental analyses, H-1, C-13, and P-31 NMR spectroscopy, as well as mass spectrometry Additionally, the structures of 2 and 12 were determined by single crystal X-ray diffraction.

Synthesis and X‐ray Structural Analysis of Airstable Bis[3‐(dimethylamino)propyl]indium DerivativesPentacoordinate, intramolecularly base‐stabilized organoindium compounds [Me2N(CH2)3]2InBr (1), [Me2N(CH2)3]2InO2‐CCF3 (2) and [Me2N(CH2)3]2InOC6F5 (3) as well as [Me2N‐(CH2)3]2InC2H5 (4), [Me2N(CH2)3]2In(i‐C3H7) (5), and [Me2N‐(CH2)3]2In(t‐C4H9) (6) have been prepared by the reaction of indium tribromide with 3‐(dimethylamino)propyllithium and of bis[3‐(dimethylamino)propyl]indium chloride with NaO2C‐CF3, LiOC6F5, C2H5MgBr, i‐C3H7MgBr, and t‐C4H9Li, respectively. The 1H‐, 13C‐, 19F‐NMR and mass spectra of the new compounds as well as the single‐crystal X‐ray structure analysis of 1 are described and discussed.

Non-pyrophoric organometallic compounds of aluminum, gallium and indium have been developed for safer application in metalorganic vapor phase epitaxy (MOVPE) of III–V semiconductor layers. They represent molecules which are inter- or intramolecular coordinatively saturated. Their physical properties can be easily varied by simple structure variations. Thus MOVPE precursors are available which are liquid at room temperature and which have already proved to be suitable for use with conventional as well as with new organic group V sources. Synthesis and epitaxy are discussed.

The intramolecularly stabilized five‐coordinated organogallium and organoindium compounds {2,6‐[(CH3)2NCH2]2C6H3H3}‐GaMe2 (1), {2,6‐[(CH3)2NCH2]2C6H3}InR2 (2–4), and {2,6‐[(C2H5)2‐NCH2]2C6H3}InEt2 (5) have been synthesized from {2,6‐bis‐[(dimethylamino)methyl]phenyl)}lithium or from {2,6‐bis[(diethylamino)methyl]phenyl}lithium and the corresponding diorganogallium or diorganoindium chloride. The 1H‐, 13C‐NMR and mass spectra of the new compounds are reported and discussed.

Intramolecularly base-stabilized four-coordinated metallacyclic organoaluminium, -gallium, and -indium compounds C5H10Al(CH2)3NMe2 (4), C4H8Ga(CH2)3NMe2 (5), C5H10Ga(CH2)3NMe2 (6), C5H10GaCH2CH(Me)CH2NMe2 (7), C4H8Ga(CH2)4NMe2 (8), C5H10Ga(CH2)4NMe2 (9), EtAl[(CH2)3]2NMe (10), MeGa[(CH2)3]2NMe (11), EtGa[(CH2)3]2NMe (12), MeIn[(CH2)3]2NMe (13), and MeIn Activated (CH2)3N(Me)CH2CH2N(Me)(CH2)2CH2 (14) have been synthesized by the reaction of [3-(dimethylamino)propyl]aluminium dichloride (1), [3-(dimethylamino)propyl]gallium dichloride (2), [3-(dimethylamino)-2-methylpropyl]gallium dichloride (3), or [4-(dimethylamino)butyl]gallium dichloride with the respective bis-Grignard reagents or by the reaction of the organometal dichlorides RMCl2 with bis[3-(chloromagnesio)propyl[methylamine or with N,N'-bis[3-(chloromagnesio)propyl]-N,N'-dimethylethylenediamine. Aluminium or gallium trichloride reacts with tris[3-(chloromagnesio)propyl]amine to give Al[(CH2)3]3N (15) and Ga[(CH2)3]3N (16). The H-1, C-13-NMR and mass spectra of the new compounds as well as the X-ray crystal structure of 16 are discussed. 4, 6, and 12 have been tested successfully as MOVPE precursors.

AbstractIntramolecularly stabilized four‐coordinated organoaluminium, ‐gallium, and‐indium compounds R2MC6H4CH2NR'2‐(2) (1–7), Me2MCH2C6H4NMe2‐(2) (8, 9), Me2MCH2C6H4CH2‐NMe2‐(2) (10, 11), and Me2GaC6H4NMe2 (12) have been synthesized from O ‐[(dialkylamino)methyl]phenyllithium, [O ‐(dimethylamino)phenyl]methyllithium, {O ‐[(dimethylamino)methyl]phenyl}methyllithium and O ‐(dimethylamino)phenyllithium, respectively. The 1H‐, 13CNMR, and mass spectra of the new compounds and the X‐ray crystal structures of 2 and 7 are reported and discussed.

Novel organogallium and organoindium compounds containing the intramolecularly stabilizing dimethylaminopropyl, diethylaminopropyl or dimethylaminobutyl ligand have been synthesized for use in MOVPE. Syntheses and NMR investigations of the moderately air-stable compounds are reported. Using those compounds, GaAs and InP semiconductor layers of good quality could be grown in initial experiments.

This paper presents proposals for the synthesis of several group III metal organics (In, Ga, Al compounds) and preliminary results on their use in the MOVPE (metal organic vapor phase epitaxy) of III-V semiconductors. The common feature of all these precursors is that they are saturated by interor intramolecular coordination. They are even non-pyrophoric and air resistant which is an interesting aspect with respect to safe handling. In addition, the compounds are liquid at room temperature with a low but sufficient vapor pressure for MOVPE without additional heating of the source.

InCl3 reacts with 2,6-[(CH3)2NCH2]2C6H3Li in hexane to yield 2,6-[(CH3)2NCH2]2C6H3InCl2 (1). The treatment of CH3InCl2 with 2,6-[(C2H5)2-NCH2]2C6H3Li affords CH32,6-[(C2H5)2NCH2]2C6H3InCl (2). Both compounds have been characterized by elemental analyses, 1H NMR, 13C NMR and mass spectra. 2 crystallizes monoclinic in the space group P21/n. The unit cell parameters are a 1090.2(1), b 1354.0(2), c 1300.0(2) pm, α 99.99(1)° and V 1.8899 × 106 pm3 with a final R value of 0.049 for all 4055 independent reflections.