Aminobis

Compounds of types i, 2, and 3 were deduced to have planar, trigonal configurations from kinetic and stereochemical observations71 however, confirmation of this postulate was provided only a few years ago by the X-ray structure analysis of (bistrimethylsilyl)aminobis(trimethylsilylimino)phosphorane8). The P/N(imine) bonds were found to be relatively short, which was attributed to a high rc-bonding component in the planar system of coordinatively unsaturated phosphorus. 

Recent research on aminocarbenes has led to the development of a very fruitful field. The synthesis of relevant complexes (Scheme 19) such as aminobis(yhde) carbene species (69) [147], cyclic C-amino P-ylides (70) (easily transformed into carbenes) [148] and their corresponding complexes (71) [149], and special ylides (72), which also transform very easily into carbenes by loss of pyridinium group, has been reported. Emphasis has been made on the transformation between ylides and carbenes and on the donor properties of the ylides. From the results obtained the ylides have shown a stronger a-donor behavior compared with the carbenes. 

Terphenyls and Derivatives. p-Terphenyl can be prepared satisfactorily in two ways (a) from the nitrosoacetyl derivative of 4-aminobi-phenyl, and (6) from the bis-nitrosoacetyl derivative of p-phenylenedi-amine. The yields by both routes are about the same (50-60%). 

Ring closure of w s-o-aminostilbene (XIX) to phenanthrene, o-aminobi-benzyl (XX) to 9,10-dihydrophenanthrene, and o-aminodiphenylmeth-ane (XXI) to fluorene can be effected likewise through the diazoniflm reaction.26 A number of substituted fluorenones have been prepared by this method.26 ... 

However, homogeneous catalysts obtained from nickel (II) complexes, e.g. bisallylnickel Ni(All)2, and bis(trimethylsilyl)aminobis (trimethylsilylimino) phosphorane (Me3Si)2NP(=NSiMe3)2 in toluene solution deserve special attention [182] ... 

The polymerisation of ethylene in the presence of an Ni(II) complex containing a ligand originating from aminobis(imino)phosphorane leads to short-chain branched polyethylene [182]. This is due to the copolymerisation of ethylene with short-chain 1-alkenes formed in such a system. 

Catalysts capable of 2, co-linkage of a-olefins are obtained from the reaction of Ni(0) or Ni(II) compounds, such as Ni(Cod)2 or Ni(All)2 respectively, with aminobis(imino)phosphorane, such as (Me3Si)2NP(=NSiMe3)2, preferably used in equimolar ratio the catalysts are characterised by the appearance of Ni(II) species as has been shown by scheme (18) [182]. 

SYNS AMINOBIS(PROPYLAMINE) BIS-(3-AMINOPROPYL)AMINE 3,3-DIAiMINODIPROPYL-AMINE 3,3 -DIAMINODIPROPYLAMINE DIPROPYLENETRIAMINE IMINOBIS(PROPYL-AMINE) 3,3 -IMINOBIS(PROPYLAMINE) 1,3-PROPANEDIAMINE, N-(3-AMINOPROPYL)- PROPYLAxMINE, 3,3 -IMINOBIS-... 

PHENYL-l,2,4-TRIAZOLE see AIXOOO AMINOBIS(PROPYLAMINE) see AIX250 AMINOBIS(PROPYLAMINE) see AIX250... 

The aminobis(imino)phosphorane P[N(SiMe3)2](NSiMc3)2 undergoes cycloaddition with EX (=A1C13, SnCU, TiCU, NbClj, or FeCU) to yield X[(Mc3Si)2N]-... 

Derivation (1) From crude anthracene cake by selective solution of the phenanthrene with crude solvent naphtha, removal of the anthracene by conversion into a sulfonic derivative, and extraction by means of water. (2) Synthetically from o-aminobi-phenyl. 

Preparation. - the first aminobis(dialkylamino)phosphines (13) have been prepared and characterised. They can be stored for weeks at low temperatures, but oligomerise slowly at room temperature in solution to 14. Some 1-methoxy-(15) and 1-dialkylaminophosphirenes (16) have been prepared from the corresponding 1-chlorophosphirenes. The first examples of bicyclophosphites... 

The reaction between ammonia (or a primary or secondary amine), formaldehyde and phosphorous acid is only one particular case of the Kabachnik-Medved -Fields reaction, consisting of the aminomethylation of a phosphorus species possessing a reactive P(0)H group, and so is of the Mannich type. The involvement of ammonia leads only to 226 and the intermediate aminomethylphosphonic 227 (R = H) and aminobis(methylene)bisphos-phonic acid 228 (R = H) are not isolable although they are detectable by NMR spectroscopy the sequence can be stopped at the earlier stages if a primary or secondary amine is used The use of a,co-diaminoalkanes leads to complexones of type 229 . Ethanolamine affords the related bis(phosphonic acid) 230 and diethanolamine yields 231 under similar conditions acidolysis of the linear compounds brings about their cyclization... 

Arsenic, chlorobis(trifiuoromethyl)-(trimethylsilyl)aminobis-, 242 Arsenic, dichlorobis(trifluoromethyl)- bis(trimethylsilyl)amino -, 242... 

Most of the nickel catalysts with anionic ligands discussed above will only dimerize a-olefins. Notable exceptions are the oligomerization of a-olefins by the aminobis(imino)phosphorane nickel catalyst (13). ... 

The nickel aminobis (imino) phosphorane catalyst polymerizes linear and singly branched a-olefins to... 

Scheme 8. 2, -Enchainment of a-Olefins by Aminobis(imino)phosphorane Nickel Catalyst...

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