Derivatives of 0 x 0 Acids Ill. Functional Derivatives. Science moves, but slowly slowly, creeping on from point to point. Alfred Lord Tennyson Several previous Notes have discussed various aspects of the inorganic 0x0 acids: 0x0 acids and their salts ( I ); some derivativesof 0x0 acids (2): . . . lower valent 0x0 acids of ohosphurus and sulfur (3);organic derivatives of 0x0 acids with an organic residue bonded directly to the central atom (4,51,and the insertion or infix pattern of nomenclature for naming derivatives of 0x0 acids (6).We would now like UJ consider in this Note, some general'aspects of nomenclature for the socalled functional derivatives of the inoraanic 0x0 acids. Functional derivatives of 0x0 acids may be defined quite generally as being derived formally by the operation of replacing oxygen atoms andlor hydroxy groups ("functions") of a parent 0x0 acid by atoms or simple groups often representing other functional compound classes, such as acid halides and halogenoids (isocyanides, azides, etc.), amides, nitrides. This definition includes the oeroxv. chaloeen and halo derivatives of 0x0 acids that were di&se"d earlie; (2a). Those functional derivatives containine amide and/or imide erouos (2b) &e especially important be&use they are the moststahie, best known. and are ootentiallv the oarents of a large number of compounds deriied by s;bsti&tion of their-hydrogen atoms. For the purposes of the following discussion, we will divide functional derivatives of the 0x0 acids into two categories, acidic functional derivatives and nonacidic functional derivatives. The former compounds have a t least one acidic group (hydroxy, hydroperoxy, and their chalogen analogs) remaining; the latter compounds have no acidic group(s) remainine. - ~ The most recent IUPAC Rules for the Nomenclature of Inorganic Chemistrv (7) include the followine examoles of acid& functional de;i"atives of 0x0 acids Sulfur Aeids FSOlOH ClS020H H2NS020H HzNNHS020H HONHS020H HOS0,OOH H&(s~o~ HzS(S)O1 Phosphorus Acids HzNP(O)(OH), (HzN)~P(O)(OH) (H0)2P(0)(OOH) HBPOSS
fluorosulfuricacid (Rule 3.33) chlorosulfwic acid (Rule 3.33) amidosulfuric acid or sulfamidic acid (Rules 3.33 & 5.34) hydrazidosulfuric acid (Rule 3.33) hydroxylamidosulfurie acid (Rule 3.33) oerommonosulfuric acid (Rule 5.22) ihiosulfurousacid (Rule 5.23) thiosulfurie acid (Rule 5.23) amidophosphorie acid or phosphoramidic acid (Rule 5.34) diamidophosphoricacid or phosphorodiamidic acid (Rnle 5.34) peroxomanophosphoric aeid (Rule 5.22) monothiophosphoric acid (Rule 5.23)
30 / Journal of Chemical Education
W. C. FERNELIUS
KURT LOENING
ROY ADAMS
Kent State Univerdty Kent, Ohio 44242
Chemical Abstracts Service Columbus, Ohio 43210
Geneva College Beaver Falls Pennsylvania 15010
Other Aeids HSCN HzCS? HNOl [H2NC0211HaAsS3 H~AsSI
thiocyanic acid (Rule 5.23) trithiocarbonic acid (Rule 5.23) peroxonitric acid (Rule 5.22) earbamate ion (Table 11, pg. 102) trithioarseniousacid (Rule 5.23) tetrathioarsenic acid (Rule 5.23)
Section C of the Rules for the Nomenclature of Organic Chemistry ( 8 ) also recognizes the names amidosulfuric acid and sulfamidic' acid (C-661); thiosulfurous and thiosulfuric acid (C-651); thiocarbonic, dithiocarbonic, and trithiocarbonic acids (C-544.1), and carbamic acid (C-431.1). In addition to these names, Section C of the Organic Rules notes the use of the names chlorosulfurous acid (C-651.1), thiocarbamic (C547.1), and carhonimidic acid (C-451.4). The e x a m ~ l e above. s exceot for sulfamidic acid (sulfamic acid), carbamic acid, carbonimidic acid, phosphoramidic acid, and phosphorodiamidic acid, illustrate what we might the traditional method of naming acidic functional derivatives of the 0x0 acids, i.e., indicating the operation of replacement of oxygen atoms by an appropriate term cited as a prefix, such as amido. chloro. thio. to the name of the oarent 0x0 acid. ~ l t h o u g hthere are no'examp~esin the rules'to illustrate two operations on the same 0x0 acid, names combining two or more prefixes have been used. Examples CIS(O)(NH)(OH) chloroimidosulfuric acid (H2N)P(S)(OH)~ amidothiophospharicacid Unfortunatelv, there has been no concerted effort to codify this traditional type of nomenclature for acidic functional derivatives of 0x0 acids, even for just the mononuclear comnounds. The other names, such as sulfamidic acid, carbonimidic acid. nhosnhoramidic acid. are illustrative of the infix or insert& type of nomenclat&e discussed previously (6). Sulfamic acid and carbamic acid can he viewed s i m ~ l as v shorter forms of sulfamidic acid and carbonamidic acid. The IUPAC Inorganic Nomenclature Rules (7) give the following names for nonacidic replacement derivatives of mononuclear 0x0 acids Amides 02NNHz nitramide (Rule 1.32) SOz(NH& sulfonyl diamide or sulfonyl diamide (Rule 5.34) PO(NH& phosphoric triamide or phosphoryl triamide (Rule 5.34) Acid Halides and Halogenoids Oxide salt names are also used for this type of compound, e.g., MoCI20z,molybdenum chloride oxide (Rule 6.42). COClp carbonyl chloride (Rule 3.32) S02(N3)2 sulfonyl diazide or sulfuryl diazide (Rule 3.32) POCI? phosphoryl chloride (Rule 5.31) PSCb thiophasphoryl chloride (Rule 3.32) NOCl nitrosyl chloride (Rule 5.31) IOzF iodyl fluoride (Rule 3.32)
Other:
PO(N) SOr(NH)
phasphoryl nitride (Rule 3.32) sulfonyl imide or sulfuryl imide (Rule 3.32)
Again, Section C of the Rules for the Nomenclature of Organic Chemistry (8) also recognize the names sulfuric diamide (C-661.1), sulfamide (C-661.3), carhonyl (di)chloride (C108.2), and the names thiocarhonyl dichloride and difluoride (C-541.1). These names all illustrate the traditional method of denoting nonacidic replacement derivatives of mononuclear 0x0 acids; i.e., the word acid is replaced by an appropriate class name, e.g., phosphoric triamide. Various modifications often occur, such as changing the "ic" ending into a "yl" endingcarhonyl chloride, phosphoryl nitride; combining the two words together with elision of one or more syllables, e.g., nitramide, sulfamide: and the use of orefixes to denote replacetneut= utller than the c l a s name, e.g, thiophosphorvl chloride, thiocarhond difluuride. Aeain, no real effort has heen made to codify this traditional approach to the naming of nonacidic replacement derivatives of mononuclear 0x0 acids. As we have seen, the traditional method for describing 0x0 acids utilizing prefixes, such as per and ortho, and the suffixes "ic" and "ous", has limitations ( I ) . Since naming derivatives of mononuclear 0x0 acids by replacement techniques depends on such traditional 0x0 acid names as parents, there are a large number of acids and acid related c o m ~ o u n d sthat cannot he named in this way. However, the IUPAC Rules for the Nomenclature of Inorganic Chemistry (7) provide numerous illustrations of the use of coordination nomenclature to provide definitive names for such acids and acid related com~ounds. as illustrated earlier (2), and by the salts below
Method (a) is most widely used; method (b) is used usually only when the functional replacement method is not applicable. Preferences for the use of coordination nomenclature expressed in the IUPAC Rules for the Nomenclature of Inorganic Chemistry (7) (see, for example, the introduction of Rule 5.2 and Rule 5.214) seem to have had little effect on present usage. Rules 2.24, 2.26, and 3.33 even express the view that the commonlv used names for acids. their anions and derivatives, may he considered as abbreviated names for the c o m ~ l e t ecoordination names: e.e.. .. . "sulfate" stands for "tetraoxosuliate", and "sulfuric acid", in the name fluurosuliuric arid. stands for "trioxosulfuric acid." Perhaus this amarent apathy is because the method has not been promoted in a maior publication. Names for derivatives of mononuclear 0x0 acids hased on organic principles of substitution, i.e.. replacement of hvdrigen atoms in parent compounds,'are quitk fare in inorganic chemical nomenclature. Names like chlorosulfonic acid, which are based on the hypothetical parent acid HS020H (cf. 9, lo), the same as for organic sulfonic acids, are not recommended in the IUPAC Inorganic Rules. The IUPAC Inorganic Nomenclature Commission has preferred that names for such compounds not he exceptions to the general pattern for functional derivatives of inorganic 0x0 acids. Names based on parent hydrides, such as pH:+,are not used for describing functional derivatives of mononuclear 0x0 acids, except for boron compounds (11); however, organic derivatives are often named as hydride derivatives, e.g., chlorodiphenylphosphine (12). Literature Cited
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I l l Ferneliur. W. C.. 1.cening. K. I. and Adamr. R. M.. CHRM. EIII'C.. ill. ,2:,llmll, Adamr. It. M...I.CHIIM. 131111C..ill.:illIlYi:ll: I21 l a ) Femeliur.\I.C.,I.cenin~.K. i l ~ l h d~, L . I : u ~ K ~ I . I:Il Fer8laIiur. W. C ,I.mning. K. I.. a n d Adnmr. In. M...l.CHEM. RllllC..iI.:illiI'Jiil. 111 Ferneiiur. \V. C.. I.uening. K. I. .. and Adorns. R. M.. .I. THEM. EIWC.. 54. 2YY1IYiil. iil R n r l i a r . W. ?.. 1.0~ning.I(. I. and Adnmr. K. M.. .I. ('HEM. ElIL1?.. 51, iliY IIYiil. ilil Fernelius. W. C.. Lmniny, K. a81d A d ~ m s .H. M.. .I. CHliM. EDII?.. Ed, lilll
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potassium (disulfido)thioaurate(l-)(Rule 7.3121 potassium pentachlorunitridoosmate(2-1 (Rule 7.312)
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lu summary, t h e n thew ;ire I\\
