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IISenpnteomobrrerg g200aa7 nniicc Volume 2 Issue 3 CCHHEEMMAn IIISnSdiTTan RRJouYYrnal Trade Science Inc.
Full Paper ICAIJ, 2(3), 2007 [139-144]
Synthesis And Investigation Of The Properties Of L-Tris (Parabenzylidene amino phenyl) Phosphite And Its Metal Carbonyl Derivatives
Akbar Raissi Shabari1, Joseph J.Pesek2*, Fariba Raissi Shabari2, Mohamad Mahdavi1 1Teacher Training University of Tehran, Faculty of Chemistry, (IRAN) 2San Jose State University, Chemistry Department, San Jose, CA 95192 (U.S.A.) E-mail : [email protected] Received: 6th February, 2007 ; Accepted: 11th February, 2007 ABSTRACT KEYWORDS
The synthesis and investigation of the properties of the Schiff base tris(para- Carbonyl stability; benzylideneaminophenyl)phosphite as well as the preparation in solution at Chiral synthesis catalyst; atmospheric pressure(under N ) of this compounds as a ligand (L) with some Spectroscopic 2 metal carbonyls(mononuclear) having the general formula shown below are characterization. described. M(CO) L ,M=Ni(0),n=4,x=1,2, M=Fe(0),n=5,x=1, M=Cr(0), n-x x n=6, x=1 L=(C H -CH=N-C H -O) P. Elemental analysis as well as infrared, 6 5 6 4 3 ultraviolet-visible and NMR spectroscopic data are also presented. 2007 Trade Science Inc. -INDIA
INTRODUCTION important role in organometallic as well as coordina- tion chemistry in general[2,3]. Of particular importance The preparation of L-tris(parabenzylidenea is that phosphite ligands as part of a metal complex minophenyl) phosphate involving the reaction of have been shown to have interesting chiral proper- parabenzylidene aminophenol with PCl proceeds in ties[4,5] and have been used as effective catalysts in 3 refluxing 1,2-C H Cl or toluene with the final prod- enantioselective synthetic processes[6,7]. 2 4 2 uct depending on the reaction conditions[1]. During Ligands having electron-donating substituents the reaction evolution of chlorine occurred and a yel- are normally strong donors. Therefore, tertiary phos- low product was obtained. This new compound was phine donates more strongly than tertiary phosphite postulated to be a potential substitute in the fabrica- to a metal, (electron effect and estimation of cone tion of certain types of rubbers, plastics and in par- angle)[8]. Coordination of the ligand to the metal, ticular, polyvinylchloride. Therefore this new synthetic usually increases the electron density of the central moiety, L=(C H -CH=N-C H -O) P, has the poten- metal atom, if only electron donation is considered. 6 5 6 4 3 tial to be used in many practical applications as a re- This observation apparently contradicts the electrone placement for a variety of materials[2,3] that are cur- utrality principal of atoms in molecules when ligands
rently in use. Another notable feature of this particu- coordinate to the electron-rich low valent metals. lar compound as a ligand is the stability of the carbon Typical examples are metal carbonyls in which the monoxide-metal bond. Such ligands could play an metal atom is frequently zero-valent. 140 Properties of tris phosphite and its metal carbonyl derivatives ICAIJ, 2(3) September 2007
Full Paper When CO coordinates to a metal by its -HOMO to be 1,2 dichloroethane with the presence of a ter- at carbon, filled metal d orbitals of the transition tiary base (pyridine). Therefore, 8.8g (44.7mmol) of metal will also overlap with the low lying -LUMO parabenzylidineaminophenol was dissolved in 60mL of CO to give -back-bonding interaction. This ef- of 1,2-dichloroethane and 3.6mL of pyridine was fect implies that CO not only donates two electrons added to the solution. The mixture was transferred to by coordination, but also receives two electrons from a 3-necked flask and 1.3ml of PCl (14.9mmol) was 3 the metal at the same time, thus stabilizing the M-CO added dropwise to the solution. The reaction was ini- bonds and weakening the CO triple bond. In the tiated under nitrogen at 55C and then was refluxed case of phosphine compounds the * and 3d orbitals at 90-950C for 1hr. The mixture was then cooled to are mixed[8]. Therefore it is the mixture of orbitals room temperature, filtered and the residue was washed which is the electron receiver. On the other hand, in several times thoroughly with water leading to the iso- phosphite compounds, * orbitals of aryl groups par- lation of the pyridinium salt. There was no tertiary ticipate in receiving electron pairs from the nonbonding base hydrolyses of the >C=N- group[3,5,6]. orbital of the central metal[8]. The long-range electronic 3(C H -CH=N-C H -OH)+PCl +3C H N (C H - 6 5 6 4 3 5 5 6 5 effects of phosphite ligands in certain metal complexes CH=N-C H O) P+3(C H -NH+Cl-) 6 4 3 5 5 have already been documented[9]. The solvent was taken off in vacuum and the residue was dissolved in a minimum amount of 1,2- EXPERIMENTAL diclroethane; then n-pentane was added dropwise to it. Tris(parabenzylideneaminophenyl) phosphite was Preparation of parabenzylidineaminophenol the yellow product that was obtained. The final yield 26g(0.13mole) of paraaminophenol was added to was 85%. The new compound started to become oily HCl(11mL, 36%, 0.13mole). The mixture was stirred at a temperature of about 40-450C and at a tempera- vigorously in an atmosphere of nitrogen at 250C for ture of about 60-630C became a clear liquid. The 30mins, until a homogenous solution was obtained[3,5]. infrared spectrum of this compound in KBr is shown Then, 19g of NaOOC-CH ·3H O(0.135mole) was in TABLE 1. 3 2 dissolved in 100mL of distilled water; this aqueous The NMR spectrum for the aromatic hydrogens solution of acetate was slowly added to the above (C-H) and the hydrogen in the >C=N-H moiety is mixture. The solution was then stirred vigorously at shown in figure 1. Analysis: Calculated for tris (para room temperature resulting in a yellow viscous pre- benzylideneaminophenyl) phosphite) C, 75.59%; H, cipitate that was filtered and collected. 4.85%; N, 6.70%. (Found: C, 75.51%; H, 5.1%; N, 6.65%) (1) HCL 36% C6H5 CH O+H2N-C6H4 OH (2) NaCH3COO.3H2O Synthesis of tris (parabenzylideneaminophenyl) C6H5 CH N-C6H4 OH phosphitetriscarbonyl Ni(0)[3,5,6] The residue was dissolved in a minimum amount 1.85g of(C H -CH=N-C H O) P(3mmol) was dis- 6 5 6 4 3 of absolute ethanol, and then distilled. Water was solved in 30ml of 1,2-diclroethane and 0.14ml of Ni added dropwise. A yellow brown residue was precipi- (CO) (3mmole) was added to the solution. The mix- 4 tated (parabenzylidine-aminophenol) and was washed ture then was stirred in an atmosphere of nitrogen on filter paper with methanol. The solid was dried and refluxed for 4hr. The mixture was cooled to room under vacuum(m.p 1780C, yield 75%). The spectrum temperature and filtered. The solution was removed of this compound contained a sharp peak at 1660cm- under vacuum and the residue was redissolved in tolu- 1 showing the presence of the >C=N group, and a ene for extraction of the ligand. The solution was then -1 showing the existence of an broad peak at 3000cm TABLE 1 OH group. Stretching Imine >C=N- 1622(cm-1) Synthesis of tris(parabenzyliden aminophenyl) frequency phosphite Aromatic C-H 3081(cm-1) Aromatic C=C 1500 (cm-1) The best solvent for this synthesis was determined Aromatic P-O-C 1185,1100,950(cm-1) Inorganic CHEAMn IIndSiaTn JRournYal ICAIJ, 2(3) September 2007 Joseph J.Pesek et al. 141
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Figure 1: The 60MHz proton NMR spectrum of tris Figure 2: The 60MHz proton NMR spectrum of tris (parabenzylideneaminophenyl) phosphite (parabenzylaminophenyl) phosphite tricarbonyl Ni(0) filtered under vacuum until a yellow precipitate was precipitate was dissolved in a minimum amount of obtained. This product became oily at about a tem- chloroform. In the latter solution, ethyl ether was perature of 45-500C and at temperature of 65-70C added dropwise to 50% of the volume of CHCl . 3 became a liquid. The infrared spectrum of this com- Excess ligand remained in the solvent mixture and pound in KBr showed two bands in the carbonyl re- the residue was separated and isolated from the so- gion; one relatively strong(E) at 2010cm-1 and other lution. This product became a clear liquid at a tem- of medium intensity(A ) and sharp band at 2085cm-1. perature of 45-500C. 1 The IR spectrum of Ni(CO) contains one strong The infrared spectrum of this compound in KBr 4 sharp[7,8,9] band(T ) at 2038cm-1. The NMR spectrum showed two bands in the carbonyl region. The new 2 of this compound is shown in figure 2. Anal: The cal- compound, L Ni(CO) , has CO stretching frequen- 2 2 culated composition for the proposed new compound cies in KBr at (A ) 2040 cm-1 and (B ) 1985cm-1. The 1 2 is C, 66.20%; H, 3.94%; N, 5.50%; mol.wt: 765. NMR spectrum for this complex is shown in figure (Found: C, 66.35%; H, 4.20%; N, 5.60%) 3. Analysis: Calculated for this new compound is C, Synthesis of bis tris(parabenzylideneamino 70.95%; H, 4.43%; N, 6.20%. (Found: C, 71.15%; H, 4.45%; N, 6.10%) phenyl)phosphitedicarbonyl Ni(0)[3,5,6] 0.761g of the complex tris(parabenzylideneamino Synthesis of tris(parabenzylideneaminophenyl) [3,5,6] phenyl) phosphitetriscarbonyl Ni(0), (1 mmol) was dis- phosphite tetracarbonyl Fe(0) solved in 40ml of chloroform and 0.619g of the new 0.42ml. of Fe(CO) (3mmole) was dissolved in 5 ligand (phosphite), (1mmol) was added to it. The mix- 30ml of pure distilled toluene and 1.827g of (C H - 6 5 ture was then vigorously stirred in an atmosphere of CH=N-C H O) P was added to it (the ligand is in- 6 4 3 nitrogen at a temperature of about 550C for 4hr. soluble in toluene). The mixture then was stirred in an atmosphere of N in darkness at reflux tempera- (C H -CH=N-C H O) P-Ni(CO) +(C H -CH=N-C H O) P 2 6 5 6 4 3 3 6 5 6 4 3 ture for 16hrs. This mixture was allowed to cool to -CO N 2 room temperature and then filtered rapidly to sepa- rate the unreacted ligand. Next, the yellow-brown [(C6H5-CH=N-C6H4O)3P]2Ni(CO)2 The mixture was then cooled to room tempera- solution was immediately by vacuum. This process removed the solvent and unreacted Fe(CO) . A dark ture and filtered. The solvent from the filtrate was 5 removed under vacuum and the residue treated with brown residue was obtained, and this material was 25mL of toluene in an atmosphere of N at a tem- dissolved in pure distilled toluene. Then n-pentane 2 was added dropwise. Fe(CO) L (brown) was precipi- perature of 250C for 90min, or until the excess of 4 LNi(CO) was redissolved in toluene; the residue tated and removed. Pentane was used for further 3 consisted of L Ni(CO) and unreacted ligand. This washing and then the product was dried. This final 2 2 Inorganic CHEAMn InIdiSanT JoRurnYal 142 Properties of tris phosphite and its metal carbonyl derivatives ICAIJ, 2(3) September 2007
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Figure 3 : The 60MHz proton NMR spectrum of bis [tris(parabenzylideneaminophenyl) phosphite]dicarbonyl Ni(0)
Figure 4 : The 60MHz proton NMR spectrum of tris(parabenzylideneaminophenyl) phosphite tetracarbonyl Fe(0) product was a viscous liquid. lar to that of the iron carbonyl complex was used: The infrared spectrum of this compound in KBr -CO (C H -CH=N-C H O) P+Cr (CO) has three bands in the carbonyl region that are re- 6 5 6 4 3 6 N2 lated to substitution in the axial position[10]. LFe(CO) [(C H -CH=N-C H O) P]Cr(CO) 4 6 5 6 4 3 5 has CO stretching frequencies at (A ) 2075cm-1, (A ) 1 1 0.224g of Cr (CO) (1mmol) was dissolved in 25mL 1990cm-1 and (E) 1960cm-1. 6 of pure toluene and 0.619g of tris (parabenzylide Fe(CO) has -CO stretching frequencies at (A) 5 neaminophenyl)phosphite(1mmol) was added to the 2028cm-1 and (E) 1994cm-1. The NMR spectrum of solution. The mixture then was stirred in an atmo- this complex is shown in figure 4. Analysis: The cal- sphere of N at reflux temperature for 14hrs. The culated elemental analysis for this new compound is 2 mixture was then cooled to room temperature (250C) C, 65.56%; H, 3.90%; N, 5.30%. (Found: C, 65.84%; and filtered. The solution was removed under vacuum H, 4.10%; N, 5.45%) Attempts to obtain L Fe(CO) 2 3 at 60-650C. The yellow residue started to become by this method were unsuccessful. oily at a temperature of about 480C, and at 650C, it Synthesis of tris(parabenzylideneaminophenyl) was a clear liquid. phosphite pentacarbonyl Cr(0) The infrared spectrum of this compound in KBr has three bands in the carbonyl region. LCr (CO) has For preparation of this compound, a method simi- 5 Inorganic CHEAMn IIndSiaTn JRournYal ICAIJ, 2(3) September 2007 Joseph J.Pesek et al. 143
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Figure 5 : The 60MHz proton NMR spectrum of tris(parabenzylideneaminophenyl) phosphite pentacarbonyl Cr(0)
CO stretching frequencies at (A ) 2080cm-1, (A ) Ligands with electron-donating substituents are 1 1 2000cm-1 and (E) 1960cm-1. Cr(CO) has a single CO generally strong donors. Thus, tris(phenylphosphite) 6 stretching band(T ) at 2000cm-1[3,10]. The NMR spec- donates less strongly than tris(parabenzylidene 1u trum of this species is shown in figure 5. Analysis: aminophenyl) phosphite to metals. As a result, metal The calculated elemental analysis for this new com- complexes with the new phosphite ligand (L=(C H - 6 5 pound is C, 65.10%; H, 3.69%; N, 5.18%. (Found: CH=N-C H -O) P) are more electron-rich than 6 4 3 C, 65.30%; H, 3.80%; N, 5.30%). Attempts to ob- the(C H -O) P analogues. Therefore such compounds 6 5 3 tain L Cr(CO) by this method were unsuccessful. are considered to be more susceptible to nucleophilic 2 4 reactions and also to have stronger basicity. INSTRUMENTATION Infrared studies of (CO) for metal carbonyl de- rivatives often give valuable information about the Infrared spectra were obtained on a Perkin-Elmer structure and bonding of complexes with phosphite. (Norwalk, CT, USA) Model 595 spectrometer. The The ligands are a weaker -acceptor than the carbo- proton NMR spectra were acquired with a Hitachi nyl group. Therefore, the CO stretching is shifted to Perkin-Elmer Model 435-1203 spectrometer in the a lower frequency. The infrared spectrum of the continuous wave mode. Ultraviolet-visble spectra were ligand (L) in KBr showed some bands in the (C H - 6 5 obtained using a Milton Roy Model Spectronic 1201 C=N-) region. The (A ) stretching vibration in the 1 (Rochester, NY) interfaced to a PC computer system. metal carbonyl derivatives is a very important factor in determining the influence of basicity and reactiv- RESULTS AND DISCUSSION ity of the ligand in this kind of organometallic com- pound[3]. A comparison of the (CO) stretching fre- In this paper the phosphorous donor ligand tris quencies of the derivatives of the different metal (parabenzylideneamino-phenyl)phosphite has been carbonyls of trisphenylphosphite with the new ligand synthesized. Then some organometallic derivatives (L) is shown in TABLE 2. of nickeltetracarbonyl, ironpentacarbonyl and chro (C H -C=N-) as an The benzylideneamino group 6 5 miumhexacarbonyl have been prepared with the gen- electron donor has influence on the electronic struc- eral formula: ture and basicity of ligand. Inductive and resonance M(CO) n-x Lx, M=Ni (0),n=4,x=1,2 , M=Fe (0),n=5,x=1 effects act opposite to each other. M=Cr (0), n=6, x=1 It appears that the resonance effects are slightly L=(C H -CH=N-C H -O) P stronger than the inductive effects. Electronic effects 6 5 6 4 3 Inorganic CHEAMn InIdiSanT JoRurnYal 144 Properties of tris phosphite and its metal carbonyl derivatives ICAIJ, 2(3) September 2007
Full Paper TABLE 2 : Carbonyl stretching frequencies of the com- results in features such as the absorption of ultra- pounds in this study violet radiation in the 230-400nm range, an amor-
LNi(CO)3 L2Ni(CO)2 phous physical state, a moderate softening tempera- L (Ligand) cm-1 cm-1 ture and a resistance to hydrolysis which constitutes A E A B 1 1 the bulk properties of the anti-oxidants. Accordingly, (PhO) P 2086.5 2018.5 2017 1999 3 in view of these properties, it is anticipated that this (C6H5-CH=N-6H4-O) 3P 2085 2015 2040 1990 LCr(CO) (cm-1) new compound can be used as a substitute in rub- L (Ligand) 5 A1 A1 E bers, plastics and especially PVC functioning as a (PhO)3P 2083 1975 1963 alternative in the formulation of these materials with (C H -CH=N-C H -O) P 2080 2000 1950 6 5 6 4 3 a variety of potential applications[16]. in tertiary phosphine ligands have been estimated by using symmetrical stretching frequencies(A ) of REFERENCES 1 Ni(CO) PR in CS [5]. The following is the empirical 3 3 2 equation for the trend: [1] M.K.Rastogi; Asian J.Chem., 9, 5 (1997). [2] G.Wood, A.E.Shaw; “Chemistry of The Elements”, i=3 1 (CO)( A1 ) 2056.1 i (cm ) Pergamon Press; New York, 591 (1985). i=1 [3] A.R.Shabari; Bull.Fac.Sci.Tehran Univ, 6, 1 (1997). where denotes a substituent parameter of R on the P atom: [4] A.C.Dros, A.Meetsma, R.M.Kellog; Tetrahedron, 55, i i for benzylideneaminophenyl is described in the following equa- 3071 (1999). tion[11]: [5] K.Nozaki, M.Yasutomi, K.Nakamoto, T.Hiyama; i=3 Polyhedron, 17, 1159 (1998). (KBr)2085( A ) 2056.1 (cm 1 ) 1 i=1 i [6] C.G.Arena, F.Faraone, C.Graiff, A.Tiripicchio; Eur.J. Inorg.Chem., 3, 711 (2002). The UV spectra of the new compounds are as [7] S.Deerenberg, O.Pamies, M.Dieguez, C.Claver, P.C. follows: Kamer, P.van Leeuwen; J.Org. Chem., 66, 7626 (2001). L LNi(CO)3 L2Ni(CO)2 LFe(CO)4 LCr(CO)5 [8] C.A.Tolman; Chem.Rev., 77, 313 (1977). 258 262 252 262 262 max(nm) [9] A.W.Baker, A.T.Shulgin; J.Am.Chem.Soc., 81, 1523 According to the UV spectra of these compounds, (1959). an increase in the (262nm) was noted in the singly [10] G.O.Spessard, G.L.Miessller; “Organometallic Chem- max istry”, Wiley; New York, 18 (1987). substituted species[12]. The value of is directly re- max [11] A.G.Orpen, N.G.Connelly; J.Chem.Soc.Chem. lated to the transitionsn * and *. In the sin- Commum., 1310 (1985). gly substituted complex, the ligand has strong -do- [12] H.Haas, R.K.Sheline; J.Chem.Phys., 47, 3001 (1967). [13] nor and weak -acceptor back-bonding . Therefore, [13] P.S.Braterman; ‘Metal Carbonyl Spectra’, APINC, a pair of non-bonding electrons will move toward the (1975). aromatic ring. This action will increase the electron [14] C.A.Tolman; J.Am.Chem.Soc., 92, 2953 (1970). density at the nickel atom, which in turn decreases [15] W.P.Jolly; ‘Comprehensive Organometallic Chemis- the energy level between* and n resulting in a shift try, Lewis-Base Nickel Carbonyl Complexes’, Wiley; to a longer (262nm)[14]. New York, 15-33 (1982). max In a doubly substituted complex the result is com- [16] E.F.Part, M.J.Kammlet; J.Org.Chem., 26, 4022 (1961). pletely the opposite. The release of the 2nd CO group [17] T.Okamoto, K.Sbudo, T.Obta; J.Am.Chem.Soc., 97, from the nickel carbonyl increases the electron den- 7184 (1975). sity of nickel atom. This effect is due to an increase [18] F.A.Cotton, C.S.Kraihanzel; J.Am.Chem.Soc., 84, 4432 (1962). of the phosphite ligand’s participation in the back- [19] R.Stork, R.Dowd; J.Am.Chem.Soc., 85, 2178 (1963). bonding of metal to ligand. As a result, the energy [20] S.K.Mlhotra, D.F.Moley, S.Johnson; J.Am.Chem.Soc., level between n and * will increase. This action re- 86, 4756 (1967). sults in a shift to a shorter (252nm) in comparison max to the phosphite ligand itself with a of 258nm[15]. max In this new compound, the simultaneous exist- ence of phosphite ester and imine functional groups Inorganic CHEAMn IIndSiaTn JRournYal