Primary and secondary aminoalkylphosphanes R2N-(CH2)m-PH2 (R2 = Me2, nBu2, C5H10, C4H8O, 2-(1-Methyl-2-pyrrolidinyl); m = 2, 3, 6, 10, 11; 1-6) or [R2N-(CH2)m]2PH (7, R2 = C5H10; m = 2) are accessible by aminoalkylation of PH3 with ω̃ -chloroalkylamines R2N-(CH2)m-Cl in the superbasic medium DMSO/KOH (DMSO = dimethylsulfoxide). By selective N-quaternization of 1, 2, 4-6 with R'I (R' = Me, CnH2n+1; n = 6-8, 12, 16, 18) in the two-phase system CH2Cl2/H2O novel primary phosphanes [R'R2N-(CH2)m-PH2]+I- (11-16f) with quaternary ammonium groups in the alkyl side chain are obtained. The water solubility of 11-16f decreases with increasing chain length (n) of R′ 11 (R = R' = Me; m = 2) shows a trans conformation at the C2H4 bridge according to an X-ray structural analysis. Protonation of 1, 2, 4, 5 with HCl affords the water-soluble hydrochlorides [HR2N-(CH2)m-PH2]+Cl- (19-22). The cationic primary phosphanes 11-16f are stable towards oxygen. By oxidation of 11 with one or two equivalents of H2O2 the primary phosphane oxide [Me3N-(CH2)2-P(O)H2]+I- (23) or the phosphonous acid [Me3N-(CH2)2- P(O)(OH)H]+I- (23a) are formed. Hofmann degradation of 11 or 16c with KOH yields phosphirane in good yields. Reaction of 1, 2, 4-6 (L) with Fe2(CO)9 at ambient temperature yields stable complexes (CO)4FeL (26-30). Under more rigorous conditions Fe3 clusters (31, 32) with free R2N groups are obtained.
with Basic P-AtomsBy stepwise aminoalkylation of PH3 with Me2N-(CH2)2-C1 in the superbasic medium DMSO/KOH the secondary phosphane [Me2N-(CH2),],PH (2) is obtained in good yields. Metallation of 2 with n-BuLi and subsequent reaction with Me2N-(CH2)2-C1 affords the basic tertiary phosphane [Me2N-(CH2),I3P (3), which on protonation with Ph3P . HBr in CH2C12 gives ([HNMe, -(CH2)2]3P)3+ 3 Br-(4a) with an extremely high solubility in water. By oxidation of 3 with H202 and N-quaternisation with Me30t BF, the cationic phosphane oxide ([Me3N-(CH2)2]3P=0)3+ 3 BF; (5a) is formed, which could, however, not be reduced with SiHC13 or Si2C16/NEt3 to the corresponding tricationic phosphane. Tertiary cationic phosphanes of type [RMe2N-(CH2)2-P(Oct),]+X-(8a, 8b, R = Me, C8HI7; X = Br, I) are accessible by free radical addition of 1-octene to 7b and 7d. Addition of formaldehyde to ?a gives the hydroxymethyl phosphane 10a. By methylation of [RMe2N-(CH2)2-PH2]tI-(7d and ?e, R = CnH2,+1, n = 8, 12) with Me1 under controlled condition and subsequent deprotonation of the phosphonium salts 12b and 12c the cationic tertiary phosphanes 13a and 13b with long alkyl side chains may be obtained in good yields.
Synthesis and Coordination Chemistry of Hemilabile P,N-Hybride Ligands with Terminal 2-Pyridyl Donor Groups*P,N-hybride ligands 1-7 containing terminal 2-pyridyl donor X = C1, Br;15, 16). An X-ray structural analysis of groups have been obtained by base-catalyzed addition of di-[NiBr(2)]+BrP (15) reveals a distorted square pyramidal coorphenylvinylphosphane or 2-vinylpyndine to primary or se-dination geometry at Ni(II), the 2-Py donor being in apical condary phosphanes [~-PY-(CH~)~-PR'H (R' = H, Ph), position with a long Ni-N bond [2.270(15) (20, 21). The structure of 20 has been determinated Py-(CH2)2-P(R')-(CH,),-PR2 (1, 3, 6) form square planar by X-ray diffraction. The ligand 3, acting in a tridentate manNi(II), Pd(II), and Pt(I1) complexes of composition MX2(L) ner, is coordinated to Rh(1) in a distorted square-planar arran-(10-14). With NiBr2 and K2MX4 the tripod type phosphane gement with a normal Rh-N distance Fur die Synthese der Liganden rnit P-C3-P-Geriist wurde ein von uns entwickeltes Verfahren eingesetzt, das auf der nucleophilen Ringoffnung der leicht zuganglichen Phosphetaniumsalze rnit Lithium-organophosphiden beruht[l61. So liefert die Umsetzung der MonolithiumderiChew.
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