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(PR3= Pme3, Pet 3, P(Ome)3; Ar = C6H5, 2,6-/-Pr2

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(PR3= Pme3, Pet 3, P(Ome)3; Ar = C6H5, 2,6-/-Pr2 314 Bull. Korean Chem. Soc. 1999, Vol. 20, No. 3 Byung-Gyu Park et al. Preparation, Structure, and Property of Re(NAr)(PR3)2Cl3, (PR3= PMe3, PEt3, P(OMe)3; Ar = C6H5, 2,6-/-Pr2-C6H3) Byung-Gyu Park, Nam-Sun Choi, and Soon W. Lee* Department of Chemistry, Sungkyunkwan University, Natural Science Campus, Suwon 440-746, Korea Received September 16, 1998 Several bisphosphine- and bisphosphite-substituted Re-imido complexes have been prepared from Re(NPh) (PPh3)2C& 1, and Re(N-C6H3-i-Pr2)2Cl3(py), 4. Compound 1 reacted with trimethyl phosphite (P(OMe)3) to give a mixture of two isomers, mer, trans-Re(NPh)(P(OMe)3)2Cl3, 2, and fac, cis-Re(NPh)(P(OMe)3)2Cl3, 2a. In this reaction, the mer,trans-isomer is a major product. Complex 1 also reacted with triethylphosphine (PEt3) to exclu­ sively give mer, trans-Re(NPh)(PEt3)2Cl3, 3. Compound 4 reacted with trimethylphosphine (PMe3) to give mertrans-Re(N-C6H3-i-Pr2)(PMe3)2Cl3, 5, which was converted to mer-Re(N-C6H3-i-Pr2)(PMe)(OPMe3)Cl3, 6, on exposure to air. Crystallographic data for 2: monoclinic space group P2i/n, a = 8.870(2) A, b = 14.393(3) A, c = 17.114(4) A, & = 101.43(2)°, Z =4, R(wR?) = 0.0521(0.1293). Crystallographic data for 5: orthorhombic space group P212121, a = 11.307(1) A, b = 11.802(1) A, c = 19.193(2) A, Z = 4, R(wR?) = 0.0250(0.0593). Crys­ tallographic data for 6: orthorhombic space group P212121, a = 14.036(4) A, b = 16.486(5) A, c = 11.397(3) A, Z =4, R(wR2)= 0.0261(0.0630). Introduction formal four-electron donor. The more common complexes of metals in a high oxidation state have a linear imido ligand Transition-metal imido complexes have been of continu­ (C). Structure C depicts an sp-hybridized nitrogen leading to ous interest.1-6 Three general types of imido complexes are an M=N triple bond (1o, 2n) and a linear M-N-R linkage, now known,1 although Cundari’s theoretical studies led to a where the nitrogen lone pair p(n) to M(d兀)donation is very conclusion that a minimum of eight resonance structures are effective. In C, the imido liagnd acts as a formal six-electron required to describe the metal imido linkage.7 The imido donor. Wigley pointed out that in cases where multiple n ligand can be considered to bond to a transition metal with donor ligands are present in the molecule, a molecular orbital one o and either one or two n bonds. Limiting valence bond approach is required to accurately describe imido bonding.1 descriptions of this interaction are shown below. Recently we have prepared several Re-imido complexes of the type Re(NPh)Cl3(PPh3)L or Re(NPh)Cl3L2 from the re­ Q y actions of Re(NPh)(PPh3)2Cl3 with small, strongly coordi­ nating ligands (L = CO, P(OMe)3, PMe3) (eq 1 and 2).17-19 M=N M=N-R ivmm-r • \ ▲ Because of our continuous interest in the complexes of this R 1 type, we tried to prepare other bisphosphine- and bisphos- A B C phite-substituted Re-imido complexes. Herein we report pre­ paration, structure, and some properties of Re(NAr)(PR3)2Cl3 [NR]2* 4e 4e 6e (PR3 = PMe3, PEt3, P(OMe) 3； Ar = C6H5, 2,6-，心2(6任). Structure A depicts an sp2-hybridized nitrogen leading to an M=N double bond (1o, 1n) and a bent M-N-R linkage with the lone pair in an N(sp2) hybrid orbital. In the closed- (1) shell formalism, the imido dianion [NR]2- in A acts as a four- electron donor. Some zero-valent metals (Cr, W) are known to possess a bent imido ligand (A).8,9 In addition, bent imido species with a formal M-N double bond are known to be more reactive than linear ones, because nucleophilic reactiv­ PMe3 Cl ity is enhanced in the bent NR ligand.10-16 Structure B PMe3 丨 .、''이 J .、''이 1 ------ 르 * ci— + cl—ReHNPh (2) depicts an sp-hybridized nitrogen with the lone pair in an Reflux Clx I M"，I N(p) atomic orbital that does not participate in the sp hybrid­ PMe3 PPh3 ization. In B, the M=N double bond (1o, 1n) is maintained if major minor symmetry restrictions or an energy mismatch with available metal orbitals does not allow donation of the lone pair on the Experimental Section nitrogen atom to the metal. In B, the imido ligand acts as a Unless otherwise stated, all the reactions have been per­ *To whom correspondence should be addressed. Tel: 0331-290­ formed with standard Schlenk line and cannula techniques 7066, Fax: 0331-290-7075, e-mail: [email protected]. under an argon atmosphere. Air-sensitive solids were manip­ Preparation, Structure, and Property ofRe(NAr)(PR 3)2(Cl3 Bull. Korean Chem. Soc. 1999, Vol. 20, No. 3 315 ulated in a glove box filled with argon. Glassware was uum to give 0.45 g (0.73 mmol, 83%) of 3. This product soaked in KOH-saturated 2-propanol for ca. 24 h and conveniently recrystallized from benzene-hexane. 1H NMR washed with distilled water and acetone before use. Glass­ (CDCl3): 8 7.738-7.263 (5H, m, phenyl), 2.210 (12H, m, ware was either flame-dried or oven-dried. Hydrocarbon sol­ PCH2CH3), 1.163 (18H, m, PCH2CH3). 13C(1H}-NMR vents were stirred over concentrated H2SO4 for ca. 48 h, (CDCl3): 8 130.2-119.8 (phenyl), 14.8 (t, Jp-c = 14.3 Hz, neutralized with K2CO3, stirred over sodium metal, and dis­ PCH2CH3), 7.4 (s, PCH2CH3). 31P(1H}-NMR (CDCl3): 8 tilled by vacuum transfer. Benzene, diethyl ether, toluene, -23.3 (s). Anal. Calcd for C18H35NP2Cl3Re: C, 34.87; H, and tetrahydrofuran (THF) were stirred over sodium metal 5.69; N, 2.26. Found: C, 35.38; H, 5.76; N, 2.02. Mp and distilled by vacuum transfer. NMR solvent (CDCl3) was (decomp.): 117-119 °C. IR (KBr): 2970, 2935, 2907, 1475, degassed by freeze-pump-thaw cycles before use and stored 1455, 1420, 1259, 1162, 780, 762, 732, 716, 691 cm-1. over molecular sieves under argon. 2,6-Diisopropylaniline Preparation of mer;trans-Re(N-C6H3或 -Pr2)(PMe3)2Cl3, (H2N-C6H3-2,6-i-Pr2) was distilled over CaHz CO (99.9%) 5. To an opaque, dark green solution of benzene (60 mL) was purchased from Union Gas company and use as receiv­ containing 0.35 g (0.48 mmol) of 4 was added 2.0 mL (2.0 ed. Re metal, trimethylphosphine (PMe3, 1 M in toluene), mmol) of PMe3 (1 M in toluene). The resulting solution was trimethyl phosphite (P(OMe)3), triethylphosphine (PEt3, 1 M allowed to stir for 12 h at room temperature, and then fil­ in THF), triphenylphosphine (PPh3), sodium cyclopentadie- tered. The solvent was removed under vacuum to give yel­ nylide (NaCp; Cp = C5H5, 2 M in THF), thallium cyclopenta- lowish green solids. The resulting solids were washed with dienylide (TlCp), sodium pentamethylcyclopentadienylide pentane (2 x 25 mL) and then dried under vacuum to give ;(NaCp* *Cp = C5Me5, 0.5 M in THF), LiBEtaH, and 0.16 g (0.26 mmol, 54%) of 5. This product mixture conve­ LiBEtaD were purchased from Aldrich company and used as niently recrystallized from benzene-pentane. 1H NMR received. Re(NPh)(PPh3)2Ck 1,20 and Re(N-C6H3-i-Pr2)2Cl3 (CDCl3): 8 7.647-7.069 (3H, m, phenyl), 3.917 (2H, m, (py), 4,21,22 were prepared by the literature methods. CHMe2), 1.642 (18H, t, Jp-h = 4.6 Hz, PMe3), 1.148 (12H, d, 1H- and 13C(1H}-NMR spectra were recorded with a J = 6.8 Hz, CHMez). 13C(1H}-NMR (CDCh): 8 152.2-125.2 Bruker AMX 500 MHz spectrometer with reference to inter­ (phenyl), 28.1 (CHMe?), 24.3 (CHMe?), 12.8 (t, Jp-c = 16.8 nal solvent resonances and reported relative to tetramethylsi­ Hz, PMe3). 31P(1H}-NMR (CDCh): 8 -40.7 (s). Anal. Calcd lane. 31P(1H}-NMR spectra were also recorded with a Bruker for C18H35NP2Cl3Re: C, 34.87; H, 5.69; N, 2.26. Found: C, AMX 500 MHz spectrometer with reference to external 34.94; H, 5.75; N, 1.83. Mp (decomp.): 207-209 °C. IR 85% H3PO4. IR spectra were recorded with a Nicolet 205 (KBr): 2955, 2912, 2867, 1587, 1414, 1359, 1284, 954, 856, FTIR spectrophotometer. Melting points were measured with 804, 762, 745, 675 cm-1. a Thomas Hoover capillary melting point apparatus without Formation of mer-Re(N-C6H3-4Pr2)(PMe3)(OPMe3)Cl3, calibration. Elemental analyses were performed by the Korea 6. When the solution of benzene-pentane containing 5 was Basic Science Center. allowed to be in contact with air for 72 h, 5 slowly trans­ Preparation of Re(NPh) (P(OMe)3)2 CI3, 2 and 2a. Heat­ formed to 6. 1H-NMR (CDCh): 8 7.583-7.026 (3H, m, phe­ ing (30 min) 2.0 g (2.2 mmol) of 1 with 1.10 mL of P(OMe)3 nyl), 3.926 (2H, m, CHMe?), 1.709 (9H, d, Jp-h = 13.0 Hz, (9.2 mmol) under reflux in benzene (60 mL) gave a green OPMe3), 1.547 (9H, Jp-h = 16.0 Hz, PMe3), 1.165 (12H, d, solution, and then the solvent was removed under vacuum to J = 6.8 Hz, CHMe2).
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