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char = p;code = 112
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char = n;code = 110
char = d;code = 100
char = e;code = 101
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char = t;code = 116
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char = r;code = 114
char = e;code = 101
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = v;code = 118
char = i;code = 105
char = t;code = 116
char = y;code = 121
char = :;code = 58
char = ;code = 32
char = s;code = 115
char = o;code = 111
char = l;code = 108
char = v;code = 118
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = a;code = 97
char = c;code = 99
char = t;code = 116
char = i;code = 105
char = v;code = 118
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
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char = v;code = 118
char = s;code = 115
char = .;code = 46
char = ;code = 32
char = s;code = 115
char = o;code = 111
char = l;code = 108
char = v;code = 118
char = e;code = 101
char = n;code = 110
char = t;code = 116
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = o;code = 111
char = r;code = 114
char = d;code = 100
char = i;code = 105
char = n;code = 110
char = a;code = 97
char = t;code = 116
char = i;code = 105
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = i;code = 105
char = n;code = 110
char = ;code = 32
char = a;code = 97
char = l;code = 108
char = k;code = 107
char = y;code = 121
char = l;code = 108
char = p;code = 112
char = h;code = 104
char = o;code = 111
char = s;code = 115
char = p;code = 112
char = h;code = 104
char = a;code = 97
char = n;code = 110
char = e;code = 101
char = ;code = 32
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
char = ;code = 32
char = c;code = 99
char = o;code = 111
char = m;code = 109
char = p;code = 112
char = l;code = 108
char = e;code = 101
char = x;code = 120
char = e;code = 101
char = s;code = 115
char = .;code = 46
result sql = Solvent dependent reactivity: solvent activation vs. solvent coordination in alkylphosphane iron complexes.
Solvent dependent reactivity: solvent activation vs. solvent coordination in alkylphosphane iron complexes.
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char = e;code = 101
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char = i;code = 105
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char = e;code = 101
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char = e;code = 101
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char = e;code = 101
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char = r;code = 114
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char = o;code = 111
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char = l;code = 108
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char = e;code = 101
char = t;code = 116
char = r;code = 114
char = a;code = 97
char = p;code = 112
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char = o;code = 111
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char = h;code = 104
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char = e;code = 101
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char = C;code = 67
char = 5;code = 53
char = H;code = 72
char = 3;code = 51
char = N;code = 78
char = [;code = 91
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char = M;code = 77
char = e;code = 101
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char = );code = 41
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char = s;code = 115
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char = e;code = 101
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char = o;code = 111
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char = y;code = 121
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char = f;code = 102
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char = b;code = 98
char = o;code = 111
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char = d;code = 100
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char = i;code = 105
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char = ;code = 32
char = t;code = 116
char = h;code = 104
char = e;code = 101
char = ;code = 32
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char = r;code = 114
char = e;code = 101
char = s;code = 115
char = e;code = 101
char = n;code = 110
char = c;code = 99
char = e;code = 101
char = ;code = 32
char = o;code = 111
char = f;code = 102
char = ;code = 32
char = i;code = 105
char = r;code = 114
char = o;code = 111
char = n;code = 110
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char = I;code = 73
char = I;code = 73
char = );code = 41
char = ;code = 32
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char = a;code = 97
char = l;code = 108
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char = s;code = 115
char = .;code = 46
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char = W;code = 87
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char = e;code = 101
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char = o;code = 111
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char = h;code = 104
char = i;code = 105
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char = c;code = 99
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char = d;code = 100
char = ,;code = 44
char = ;code = 32
char = M;code = 77
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char = O;code = 79
char = H;code = 72
char = ,;code = 44
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char = a;code = 97
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char = d;code = 100
char = ;code = 32
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char = o;code = 111
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char = a;code = 97
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char = o;code = 111
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char = t;code = 116
char = e;code = 101
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char = o;code = 111
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char = h;code = 104
char = a;code = 97
char = n;code = 110
char = e;code = 101
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char = ;code = 32
char = T;code = 84
char = h;code = 104
char = e;code = 101
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char = r;code = 114
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char = s;code = 115
char = u;code = 117
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char = t;code = 116
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char = ;code = 32
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char = c;code = 99
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char = ;code = 32
char = (;code = 40
char = t;code = 116
char = e;code = 101
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char = r;code = 114
char = a;code = 97
char = f;code = 102
char = l;code = 108
char = u;code = 117
char = o;code = 111
char = r;code = 114
char = o;code = 111
char = b;code = 98
char = o;code = 111
char = r;code = 114
char = a;code = 97
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char = e;code = 101
char = ;code = 32
char = a;code = 97
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char = d;code = 100
char = ;code = 32
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char = e;code = 101
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char = c;code = 99
char = h;code = 104
char = l;code = 108
char = o;code = 111
char = r;code = 114
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char = t;code = 116
char = e;code = 101
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char = a;code = 97
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char = s;code = 115
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char = a;code = 97
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char = l;code = 108
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char = e;code = 101
char = ;code = 32
char = l;code = 108
char = i;code = 105
char = g;code = 103
char = a;code = 97
char = n;code = 110
char = d;code = 100
char = ;code = 32
char = i;code = 105
char = n;code = 110
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char = h;code = 104
char = i;code = 105
char = c;code = 99
char = h;code = 104
char = ;code = 32
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result sql = The pyridine-derived tetrapodal tetraphosphane C5H3N[CMe(CH2PMe2)2]2 is susceptible to selective protonolysis of a phosphorus-carbon bond in the presence of iron(II) salts. Water produces dimethylphosphinic acid, Me2POH, and protonates the anionic remainder of the tetraphosphane. The resulting iron(II) complexes and (tetrafluoroborate and perchlorate salts, respectively) contain the residual chelate ligand in which a methyl group, derived from the ligand skeleton, is in agostic interaction with the metal centre, and in which Me2POH, unavailable in the free state owing to rapid tautomerisation, is metal-coordinated and thus stabilised. Full NMR details are presented, including 31P simulations. The reactivity towards alcohols is similar (compounds), and has been studied using deuterium labels (NMR). P-C bond cleavage may be suppressed only if all protic agents are rigorously excluded, as in the reaction of with Fe(SO3CF3)2.2CH3CN in acetonitrile solution, which produces the complex [Fe(NCMe)](SO3CF3)2. In it, the ligand acts as an NP4 coordination cap but is severely distorted from square-pyramidal geometry. The reaction of with anhydrous ferrous bromide, FeBr2, in methanol again produces a dimethylphosphinic acid ester ligand, but the complex now contains ferric iron coordinated by a carbanionic residual chelate ligand, implicating H+ as the oxidising agent under these conditions. Full spectroscopic and X-ray structural details are presented for all compounds.

Publication: Dalton Trans 2006 Dec 21 ;(47)::5583-92.
Publication Date: 2006 Dec 21
Study Author(s): Kohl, Stephan W;Heinemann, Frank W;Hummert, Markus;Bauer, Walter;Grohmann, Andreas;
Institution: Technische Universität Berlin, Institut für Chemie, Sekretariat C2, Strasse des 17. Juni 135, D-10623, Berlin, Germany.
Shortcut link to this study:
The pyridine-derived tetrapodal tetraphosphane C5H3N[CMe(CH2PMe2)2]2 is susceptible to selective protonolysis of a phosphorus-carbon bond in the presence of iron(II) salts. Water produces dimethylphosphinic acid, Me2POH, and protonates the anionic remainder of the tetraphosphane. The resulting iron(II) complexes and (tetrafluoroborate and perchlorate salts, respectively) contain the residual chelate ligand in which a methyl group, derived from the ligand skeleton, is in agostic interaction with the metal centre, and in which Me2POH, unavailable in the free state owing to rapid tautomerisation, is metal-coordinated and thus stabilised. Full NMR details are presented, including 31P simulations. The reactivity towards alcohols is similar (compounds), and has been studied using deuterium labels (NMR). P-C bond cleavage may be suppressed only if all protic agents are rigorously excluded, as in the reaction of with Fe(SO3CF3)2.2CH3CN in acetonitrile solution, which produces the complex [Fe(NCMe)](SO3CF3)2. In it, the ligand acts as an NP4 coordination cap but is severely distorted from square-pyramidal geometry. The reaction of with anhydrous ferrous bromide, FeBr2, in methanol again produces a dimethylphosphinic acid ester ligand, but the complex now contains ferric iron coordinated by a carbanionic residual chelate ligand, implicating H+ as the oxidising agent under these conditions. Full spectroscopic and X-ray structural details are presented for all compounds.
PMID: 17225895

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