Reactions of (O=)PH(OCH2CH3)2and BrMg(CH2)
- NSF-PAR ID:
- 10163881
- Date Published:
- Journal Name:
- Dalton Transactions
- Volume:
- 45
- Issue:
- 41
- ISSN:
- 1477-9226
- Page Range / eLocation ID:
- 16190 to 16204
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract m CH=CH2(4.9–3.2 equiv;m =4 (a ), 5 (b ), 6 (c )) give the dialkylphosphine oxides (O=)PH[(CH2)m CH=CH2]2(2 a –c ; 77–81 % after workup), which are treated with NaH and then α,ω‐dibromides Br(CH2)n Br (0.49–0.32 equiv;n =8 (a′ ), 10 (b′ ), 12 (c′ ), 14 (d′ )) to yield the bis(trialkylphosphine oxides) [H2C=CH(CH2)m ]2P(=O)(CH2)n (O=)P[(CH2)m CH=CH2]2(3 ab′ ,3 bc′ ,3 cd′ ,3 ca′ ; 79–84 %). Reactions of3 bc′ and3 ca′ with Grubbs’ first‐generation catalyst and then H2/PtO2afford the dibridgehead diphosphine dioxides( 4 bc′ ,4 ca′ ; 14–19 %,n′ =2m +2);31P NMR spectra show two stereoisomeric species (ca. 70:30). Crystal structures of two isomers of the latter are obtained,out ,out ‐4 ca′ and a conformer ofin ,out ‐4 ca′ that features crossed chains, such that the (O=)P vectors appearout ,out . Whereas4 bc′ resists crystallization, a byproduct derived from an alternative metathesis mode, (CH2)12P (=O)(CH2)12(O=)P(C H2)12, as well as3 ab′ and3 bc′ , are structurally characterized. The efficiencies of other routes to dibridgehead diphosphorus compounds are compared. -
Two routes to the title compounds are evaluated. First, a ca. 0.01 M CH 2 Cl 2 solution of H 3 B·P((CH 2 ) 6 CH=CH 2 ) 3 ( 1 ·BH 3 ) is treated with 5 mol % of Grubbs' first generation catalyst (0 °C to reflux), followed by H 2 (5 bar) and Wilkinson's catalyst (55 °C). Column chromatography affords H 3 B·P( n- C 8 H 17 ) 3 (1%), H 3 B· P ((CH 2 ) 13 C H 2 )( n -C 8 H 17 ) (8%; see text for tie bars that indicate additional phosphorus–carbon linkages, which are coded in the abstract with italics), H 3 B· P ((CH 2 ) 13 C H 2 )((CH 2 ) 14 ) P ((CH 2 ) 13 C H 2 )·BH 3 ( 6 ·2BH 3 , 10%), in,out -H 3 B·P((CH 2 ) 14 ) 3 P·BH 3 ( in,out - 2 ·2BH 3 , 4%) and the stereoisomer ( in,in / out,out )- 2 ·2BH 3 (2%). Four of these structures are verified by independent syntheses. Second, 1,14-tetradecanedioic acid is converted (reduction, bromination, Arbuzov reaction, LiAlH 4 ) to H 2 P((CH 2 ) 14 )PH 2 ( 10 ; 76% overall yield). The reaction with H 3 B·SMe 2 gives 10 ·2BH 3 , which is treated with n -BuLi (4.4 equiv) and Br(CH 2 ) 6 CH=CH 2 (4.0 equiv) to afford the tetraalkenyl precursor (H 2 C=CH(CH 2 ) 6 ) 2 (H 3 B)P((CH 2 ) 14 )P(BH 3 )((CH 2 ) 6 CH=CH 2 ) 2 ( 11 ·2BH 3 ; 18%). Alternative approaches to 11 ·2BH 3 (e.g., via 11 ) were unsuccessful. An analogous metathesis/hydrogenation/chromatography sequence with 11 ·2BH 3 (0.0010 M in CH 2 Cl 2 ) gives 6 ·2BH 3 (5%), in,out - 2 ·2BH 3 (6%), and ( in,in / out,out )- 2 ·2BH 3 (7%). Despite the doubled yield of 2 ·2BH 3 , the longer synthesis of 11 ·2BH 3 vs 1 ·BH 3 renders the two routes a toss-up; neither compares favorably with precious metal templated syntheses.more » « less
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The diphosphine complexes cis - or trans -PtCl 2 (P((CH 2 ) n ) 3 P) ( n = b/12, c/14, d/16, e/18) are demetalated by MCX nucleophiles to give the title compounds (P((CH 2 ) n ) 3 )P (3b–e, 91–71%). These “empty cages” react with PdCl 2 or PtCl 2 sources to afford trans -MCl 2 (P((CH 2 ) n ) 3 P). Low temperature 31 P NMR spectra of 3b and c show two rapidly equilibrating species (3b, 86 : 14; 3c, 97 : 3), assigned based upon computational data to in , in (major) and out , out isomers. These interconvert by homeomorphic isomerizations, akin to turning articles of clothing inside out (3b/c: Δ H ‡ 7.3/8.2 kcal mol −1 , Δ S ‡ −19.4/−11.8 eu, minor to major). At 150 °C, 3b, c, e epimerize to (60–51) : (40–49) mixtures of ( in , in / out , out ) : in , out isomers, which are separated via the bis(borane) adducts 3b, c, e·2BH 3 . The configurational stabilities of in , out -3b, c, e preclude phosphorus inversion in the interconversion of in , in and out , out isomers. Low temperature 31 P NMR spectra of in , out -3b, c reveal degenerate in , out / out , in homeomorphic isomerizations (Δ G ‡Tc 12.1, 8.5 kcal mol −1 ). When ( in , in / out , out )-3b, c, e are crystallized, out , out isomers are obtained, despite the preference for in , in isomers in solution. The lattice structures are analyzed, and the D 3 symmetry of out , out -3c enables a particularly favorable packing motif. Similarly, ( in , in / out , out )-3c, e·2BH 3 crystallize in out , out conformations, the former with a cycloalkane solvent guest inside.more » « less
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The model reactions CH3X + (NH—CH=O)M ➔ CH3—NH—NH═O or NH═CH—O—CH3 + MX (M = none, Li, Na, K, Ag, Cu; X = F, Cl, Br) are investigated to demonstrate the feasibility of Marcus theory and the hard and soft acids and bases (HSAB) principle in predicting the reactivity of ambident nucleophiles. The delocalization indices (DI) are defined in the framework of the quantum theory of atoms in molecules (QT‐AIM), and are used as the scale of softness in the HSAB principle. To react with the ambident nucleophile NH═CH—O−, the carbocation H3C+from CH3X (F, Cl, Br) is actually a borderline acid according to the DI values of the forming C…N and C…O bonds in the transition states (between 0.25 and 0.49), while the counter ions are divided into three groups according to the DI values of weak interactions involving M (M…X, M…N, and M…O): group I (M = none, and Me4N) basically show zero DI values; group II species (M = Li, Na, and K) have noticeable DI values but the magnitudes are usually less than 0.15; and group III species (M = Ag and Cu(I)) have significant DI values (0.30–0.61). On a relative basis, H3C+is a soft acid with respect to group I and group II counter ions, and a hard acid with respect to group III counter ions. Therefore, N‐regioselectivity is found in the presence of group I and group II counter ions (M = Me4N, Li, Na, K), while O‐regioselectivity is observed in the presence of the group III counter ions (M = Ag, and Cu(I)). The hardness of atoms, groups, and molecules is also calculated with new functions that depend on ionization potential (
I ) and electron affinity (A ) and use the atomic charges obtained from localization indices (LI), so that the regioselectivity is explained by the atomic hardness of reactive nitrogen atoms in the transition states according to the maximum hardness principle (MHP). The exact Marcus equation is derived from the simple harmonic potential energy parabola, so that the concepts of activation free energy, intrinsic activation barrier, and reaction energy are completely connected. The required intrinsic activation barriers can be either estimated fromab initio calculations on reactant, transition state, and product of the model reactions, or calculated from identity reactions. The counter ions stabilize the reactant through bridging N‐ and O‐site of reactant of identity reactions, so that the intrinsic barriers for the salts are higher than those for free ambident anions, which is explained by the increased reorganization parameter Δr . The proper application of Marcus theory should quantitatively consider all three terms of Marcus equation, and reliably represent the results with potential energy parabolas for reactants and all products. For the model reactions, both Marcus theory and HSAB principle/MHP principle predict the N‐regioselectivity when M = none, Me4N, Li, Na, K, and the O‐regioselectivity when M = Ag and Cu(I). © 2019 Wiley Periodicals, Inc. -
Abstract A new series of mono‐ and bis‐alkynyl CoIII(TIM) complexes (TIM=2,3,9,10‐tetramethyl‐1,4,8,11‐tetraazacyclotetradeca‐1,3,8,10‐tetraene) is reported herein. The
trans ‐[Co(TIM)(C2R)Cl]+complexes were prepared from the reaction betweentrans ‐[Co(TIM)Cl2]PF6and HC2R (R=tri(isopropyl)silyl or TIPS (1 ), ‐C6H4‐4‐tBu (2 ), ‐C6H4‐4‐NO2(3 a ), andN ‐mesityl‐1,8‐naphthalimide or NAPMes(4 a )) in the presence of Et3N. The intermediate complexes of the typetrans ‐[Co(TIM)(C2R)(NCMe)](PF6)(OTf),3 b and4 b , were obtained by treating3 a and4 a , respectively, with AgOTf in CH3CN. Furthermore, bis‐alkynyltrans ‐[Co(TIM)(C2R)2]PF6complexes,3 c and4 c , were generated following a second dehydrohalogenation reaction between3 b and4 b , respectively, and the appropriate HC2R in the presence of Et3N. These new complexes have been characterized using X‐ray diffraction (2 ,3 a ,4 a , and4 c ), IR,1H NMR, UV/Vis spectroscopy, fluorescent spectroscopy (4 c ), and cyclic voltammetry.