1. Polyhedral-based nonlinear optical materials. 3. Synthetic studies of cyclopentadiene- and cycloheptatriene-substituted polyhedral compounds: synthesis of 1,12-[C(7)H(7)C(2)B(10)H(10)(C(5)H(3)Me(2))] and related species
J Taylor, J Caruso, A Newlon, U Englich, K Ruhlandt-Senge, J T Spencer Inorg Chem. 2001 Jul 2;40(14):3381-8. doi: 10.1021/ic000777t.
The synthesis and characterization of a series of new olefin-substituted closo-1,12-[C(2)B(10)H(12)] compounds is described. The reaction of deprotonated closo-1,12-dicarbadodecaborane with 7-methoxycycloheptatriene yields the cycloheptatriene-substituted carborane compound, closo-[1-(1-C(7)H(7))-12-(H)-C(2)B(10)H(10)] (3). Deprotonation of 3 with butyllithium and subsequent reaction with 3,4-dimethyl-2-cyclopenten-1-one was found to yield the bis-olefin-substituted carbinol compound [1-(1-C(7)H(7))-12-(C(5)H(4)-1-(OH)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (5) in good yield. Acidic dehydration of 5 quantitatively converted it into the simple bis-olefin cage compound [1-(1-C(7)H(7))-12-(C(5)H(3)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (6). Finally, thermal treatment of 6 in refluxing toluene was employed to prepare the isomerized cycloheptatriene compound [1-(4-C(7)H(7))-12-(C(5)H(3)-3,4-(CH(3))(2))-C(2)B(10)H(10)] (7) in high yield. These compounds represent the first metal-free cyclopentadiene and bis-olefin large cluster species reported in which the C(5) ring is attached directly to the cage. The complete characterization of products by multinuclear NMR ((1)H, (11)B, and (13)C), infrared, UV-visible, and mass spectroscopic analyses is presented. The X-ray crystal structures of 3 and 7 are also reported. X-ray data for 3: triclinic system, space group P&onemacr; with cell constants a = 6.6807(3) A, b = 10.2939(3) A, c = 10.3962(4) A, alpha = 89.342(2) degrees, beta = 74.610(2) degrees, gamma = 83.373(2) degrees, Z = 2, R1 = 0.0487 (wR2 (all data) = 0.1272). X-ray data for 7: monoclinic system, space group P2(1)/c with cell constants a = 7.7207(7) A, b = 15.8730(14) A, c = 15.5493(13) A, beta = 99.146(2) degrees, Z = 4, R1 = 0.0761 (wR2 (all data) = 0.2050).
2. Synthesis, XRD Studies and NLO Properties of [ p-H2NC6H4CH2NH3][B5O6(OH)4]·1/2H2O and NLO Properties of Some Related Pentaborate(1-) Salts
Michael A Beckett, Simon J Coles, Peter N Horton, Charlotte L Jones, Kerstin Krueger J Clust Sci. 2017;28(4):2087-2095. doi: 10.1007/s10876-017-1205-1. Epub 2017 Apr 1.
The non-metal cation pentaborate(1-) salt [p-H2NC6H4CH2NH3][B5O6(OH)4]·1/2H2O (1) was synthesised from B(OH)3 and p-H2NC6H4CH2NH2 and crystallized from aqueous solution. Compound 1 was characterized by thermal (TGA/DSC), spectroscopic (IR, NMR) and single-crystal X-ray diffraction methods and it was found to crystallize in the non-centrosymmetric point group P21. Powder SHG measurements on 1 and some related alkylammonium pentaborate salts, [NH3CMe2(CH2OH)][B5O6(OH)4], [NH3CMe(CH2OH)2][B5O6(OH)4] and [NH3CHMeCH2OH][B5O6(OH)4], a substituted imidazolium salt, [1,2,3-Me3C3H2N2][B5O6(OH)4], a substituted piperidinium salt, [(CH2)5NH(CH2CH2OH)][B5O6(OH)4], and a substituted pyrrolidinium salt, [S-(+)-2-(HOCH2)C4H7NH2][B5O6(OH)4], were determined. Compound 1 and all compounds, except [1,2,3-Me3C3H2N2][B5O6(OH)4], showed some weak SHG activity with SHG efficiencies of 0.1-0.2 relative to that of KH2PO4 (KDP).
3. Low-Dimensional Architectures in Isomeric cis-PtCl2{Ph2PCH2N(Ar)CH2PPh2} Complexes Using Regioselective-N(Aryl)-Group Manipulation
Peter De'Ath, Mark R J Elsegood, Noelia M Sanchez-Ballester, Martin B Smith Molecules. 2021 Nov 11;26(22):6809. doi: 10.3390/molecules26226809.
The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to PtII, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type Ph2PCH2N(Ar)CH2PPh2 [1a-e; Ar = C6H3(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands Ph2PCH2N{CH2C(O)NH(Ar)}CH2PPh2 [2a-e; Ar = C6H3(Me)(OH)], were synthesised by reaction of Ph2PCH2OH and the appropriate amine in CH3OH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines Ph2PCH2N{CH2C(O)NH(Ar)}CH2PPh2 [2f, Ar = 3-C6H4(OH); 2g, Ar = 4-C6H4(OH)] and Ph2PCH2N(Ar)CH2PPh2 [3, Ar = 3-C6H4(OH)] were also prepared for comparative purposes. Reactions of 1a-e, 2a-g, or 3 with PtCl2(η4-cod) afforded the corresponding square-planar complexes 4a-e, 5a-g, and 6 in good to high isolated yields. All new compounds were characterised using a range of spectroscopic (1H, 31P{1H}, FT-IR) and analytical techniques. Single crystal X-ray structures have been determined for 1a, 1b∙CH3OH, 2f∙CH3OH, 2g, 3, 4b∙(CH3)2SO, 4c∙CHCl3, 4d∙½Et2O, 4e∙½CHCl3∙½CH3OH, 5a∙½Et2O, 5b, 5c∙¼H2O, 5d∙Et2O, and 6∙(CH3)2SO. The free phenolic group in 1b∙CH3OH, 2f∙CH3OH,2g, 4b∙(CH3)2SO, 5a∙½Et2O, 5c∙¼H2O, and 6∙(CH3)2SO exhibits various intra- or intermolecular O-H∙∙∙X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements.
