321991-75-7

Upstream product

• 1333-74-0 hydrogen 
• 77347-62-7 [(μ-chloro)2(tetrahydrothiophene)2(pentafluorophenyl)2(platinum(II))2] 
• 321991-73-5 di-oct-7-enyl-phenyl-phosphane 

Relevant academic research and scientific papers

Partially Shielded Fe(CO)3 Rotors: Syntheses, Structures, and Dynamic Properties of Complexes with Doubly trans Spanning Diphosphines, trans- Fe(CO)3(PhP((CH2)n)2 PPh)

Reactions of Fe(CO)3(n4-benzylideneacetone) and PhP((CH2)mCH=CH2)2 (m = a, 4; b, 5; c, 6) give trans-Fe(CO)3(PhP((CH2)mCH=CH2)2)2 (2a-c, 28-70%), which are treated with Grubbs' catalyst (15 mol %; refluxing CH2Cl2). NMR analyses of the crude interligand metathesis products trans-Fe(CO)3(PhP((CH2)mCH=CH(CH2)m)2PPh) (3a-c, 30-31%) suggest Z/E C=C mixtures and/or byproducts from intraligand metathesis or oligomers. Subsequent hydrogenations (5 bar/cat. Rh(Cl)(PPh3)3 or PtO2) afford trans-Fe(CO)3(PhP((CH2)n)2PPh) (4a-c, 69-77%; n = 2m + 2, synperiplanar phenyl groups), which density functional theory calculations show to be more stable than isomers derived from other metathesis modes. Crystallizations give (E,E)-3a and 4b, the X-ray structures of which are determined and analyzed. Variableerature 13C{1H} NMR experiments show that rotation of the Fe(CO)3 moiety in 4b is rapid on the NMR time scale (RT to 0 °C; δG?273 K ≤ 12.8 kcal/mol), but that in 4a is not (RT to 105 °C; δG?378 K ≥ 17.9 kcal/mol). These data indicate rotational barriers lower than those in analogues in which three methylene chains connect the phosphorus atoms, trans-Fe(CO)3(P((CH2)n)3P).

Alkene metatheses in transition metal coordination spheres: Dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

The alkene-containing phosphines PPh((CH2)nCH=CH 2)2)2 (4) are prepared from PPhH2, n-BuLi, and the corresponding bromoalkenes (1: 2 : 2), and combined with the platinum tetrahydrothiophene complex [Pt(μ-Cl)(C6F 5)(S(CH2CH2-)2)]2 (12) to give the square-planar adducts trans-(Cl)(C6F5) Pt(PPh((CH2)nCH=CH2)2)2 (11, 93-73%; n = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs' catalyst (2) are studied. With 11e, two isomers of trans-(Cl)(C6F5)Pt(PPh(CH2) 14P(CH2)14Ph) (15e) are isolated after hydrogenation. Both form via dimacrocyclization between the trans-phosphine ligands, but differ in the dispositions of the PPh rings (syn, 31%; anti, 7%). The alternative intraligand metathesis product trans-(Cl)(C6F 5)Pt(PPh(CH2)14)2 (16e) is independently prepared by (i) protecting 4e as a borane adduct, H 3B·PPh((CH2)6CH=CH2) 2, (ii) cyclization with 2 and hydrogenation to give H 3B·PPh(CH2)14, (iii) deprotection and reaction with 12. The sample derived from lie contains ≤2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of syn-15e, anti-15e and 16e are verified crystallographically, and the macrocycle conformations analyzed. As expected from the (CH2)n segment length, 11a undergoes intraligand metathesis to give (Z,Z)-trans-(Cl)(C6F5)Pt(PPh(CH2) 2CH=CH(CH2)2)2 (86%), as confirmed by a crystal structure of the hydrogenation product. Although lib does not yield tractable products, 11c gives syn-(E,E)-trans-(Cl)(C6F 5)Pt(PPh(CH2)4CH=CH(CH2) 4P(CH2)4CH=CH(CH2)4Ph) (21%). This structure, and that of the hydrogenation product (syn-15c; 95%), are verified crystallographically. Analogous sequences with 11d,f give syn-15d,f (5 and 14% overall).

Olefin metatheses in metal coordination spheres: Novel trans-spanning bidentate and facially-spanning tridentate macrocyclic phosphine complexes

The title reaction is applied to square-planar rhodium and platinum complexes with trans PPh2(CH2)6CH=CH2 ligands, and square-planar platinum or octahedral tungsten complexes with trans or facial PPh[(CH2/